US20140216506A1 - Substrate processing apparatus - Google Patents

Abstract

There is provided a substrate processing apparatus including: a substrate holder configured to hold a substrate on which a resist pattern is formed; a rinse solution supply unit configured to supply a rinse solution onto the substrate held by the substrate holder; a vapor supply unit configured to supply vapor of a first processing solution, which hydrophobicizes the resist pattern, onto the substrate on which the rinse solution is supplied from the rinse solution supply unit; and a rinse solution removing unit configured to remove the rinse solution from the substrate in an atmosphere including the vapor of the first processing solution supplied from the vapor supply unit.

Description

CROSS-REFERENCE TO RELATED APPLICATION
• This is a divisional application of U.S. patent application Ser. No. 12/974,092, filed on Dec. 21, 2010 which claims the benefit of Japanese Patent Application No. 2009-295390 filed on Dec. 25, 2009, the entire disclosures of which are incorporated herein by reference.
FIELD OF THE INVENTION
• The present disclosure relates to a substrate processing apparatus for processing a substrate by using a processing solution.
BACKGROUND OF THE INVENTION
• In a photolithography process for manufacturing a semiconductor device, photoresist is coated on a surface of a semiconductor substrate (hereinafter, simply referred to as a “substrate” or a “wafer”), and a mask pattern is exposed on the photoresist and then is developed, so that a resist pattern is formed on the surface of the wafer.
• In such a photolithography process, a developing process may be performed by, e.g., a puddle method or a dipping method. By way of example, in the puddle method, the developing process is performed by supplying a developing solution to the wafer, whereas in the dipping method, the developing process is performed by submerging the wafer in the developing solution. Then, in both methods, a rinse solution such as pure water which is used as a cleaning solution is supplied to the wafer to wash away the developing solution. Thereafter, to remove the rinse solution from the wafer, a drying process is performed by blowing air to the wafer or by rotating the wafer.
• Meanwhile, along with the recent trend for higher degree of miniaturization of semiconductor devices, resist patterns are getting finer and becoming to have a higher aspect ratio. Since such resist patterns are microscopic and have a high aspect ratio, when the rinse solution is removed from between the patterns during the drying process, an attraction force may be generated between the patterns due to a surface tension of the rinse solution, thereby resulting in a so-called “pattern collapse”. In order to prevent the pattern collapse, there has been proposed a developing method for supplying, onto a substrate, an organic solvent having a smaller surface tension than that of the rinse solution before the drying process is performed.
• By way of example, in order to prevent pattern collapse in the process of removing a rinse solution, there has been proposed a developing method for supplying a rinse solution to a substrate having a developed resist pattern and supplying a fluorine-containing organic solvent to the substrate onto which the rinse solution has been supplied (see, for example, Patent Document 1).
• Patent Document 1: Japanese Patent Laid-open Publication No. 2003-178943
• However, when a processing solution containing the organic solvent is supplied to the substrate onto which the rinse solution has been supplied, the following problems may be caused.
• As a next-generation exposure technology, EUV (Extreme Ultra-Violet) exposure is under development, and further miniaturization of a resist pattern is progressing. Besides, when an etching is performed using the miniaturized resist pattern as a mask to transfer the resist pattern onto an etching target film under the resist pattern, there may be a case in which a height of a resist pattern is increased depending on etching conditions. If the height of the resist pattern increases, an aspect ratio with respect to a width of the resist pattern may also be increased. Such an increase of the aspect ratio of the resist pattern may cause pattern collapse depending on a relationship between a surface tension of pure water and a contact angle of the pure water with respect to the resist pattern, when the water is removed from the resist pattern during the drying process after the developing process and the rinse process.
• It has been attempted to prevent pattern collapse by hydrophobicizing a surface of a resist pattern through the use of a hydrophobicizing agent instead of the processing solution including the fluorine-containing organic solvent. Since, however, the hydrophobicizing solution is a high-price liquid chemical, cost for processing the substrate may be increased.
• Furthermore, the pattern collapse may occur not only in the developing process but also in various subsequence substrate processes performed after the resist pattern is developed. For example, the pattern collapse may occur in a cleaning process for cleaning the substrate on which the resist pattern is formed.
BRIEF SUMMARY OF THE INVENTION
• In view of the foregoing, the present disclosure provides a substrate processing apparatus capable of preventing pattern collapse when a rinse solution is removed from a substrate on which a microscopic resist pattern is formed and also capable of reducing cost for processing the substrate by decreasing an amount of usage of a hydrophobicizing agent.
• To solve the aforementioned problems, the following means have been devised in accordance with the present disclosure.
• In accordance with one aspect of the present disclosure, there is provided a substrate processing method including: a rinse solution supply process for supplying a rinse solution onto a substrate on which a resist pattern is formed; and a rinse solution removing process for removing the rinse solution from the substrate in an atmosphere including vapor of a first processing solution that hydrophobicizes the resist pattern.
• In accordance with another aspect of the present disclosure, there is provided a substrate processing apparatus including: a substrate holder configured to hold a substrate on which a resist pattern is formed; a rinse solution supply unit configured to supply a rinse solution onto the substrate held by the substrate holder; a vapor supply unit configured to supply vapor of a first processing solution, which hydrophobicizes the resist pattern, onto the substrate on which the rinse solution is supplied from the rinse solution supply unit; and a rinse solution removing unit configured to remove the rinse solution from the substrate in an atmosphere including the vapor of the first processing solution supplied from the vapor supply unit.
• In accordance with the present disclosure, pattern collapse can be prevented when a rinse solution is removed from a substrate on which a microscopic resist pattern is formed, and cost for processing the substrate can be reduced by decreasing an amount of usage of a hydrophobicizing agent.
BRIEF DESCRIPTION OF THE DRAWINGS
• Non-limiting and non-exhaustive embodiments will be described in conjunction with the accompanying drawings. Understanding that these drawings depict only several embodiments in accordance with the disclosure and are, therefore, not to be intended to limit its scope, the disclosure will be described with specificity and detail through use of the accompanying drawings, in which:
• FIG. 1 is a plane view of a coating and developing system including a developing apparatus in accordance with a first embodiment of the present disclosure;
• FIG. 2 is a front view of the coating and developing system shown inFIG. 1;
• FIG. 3 is a rear view of the coating and developing system shown inFIG. 1;
• FIG. 4 is a plane view of a developing unit in accordance with the first embodiment;
• FIG. 5 is a cross sectional view of the developing unit shown inFIG. 4;
• FIG. 6 is a diagram schematically illustrating major parts of the developing unit in accordance with the first embodiment;
• FIG. 7 provides a flowchart for describing a process sequence of a developing method using the developing unit;
• FIGS. 8A to 8D are first side views for illustrating respective processes of the developing method using the developing unit;
• FIGS. 9A to 9D are second side views for illustrating respective processes of the developing method using the developing unit;
• FIGS. 10A to 10D are third side views for illustrating respective processes of the developing method using the developing unit;
• FIG. 11 is a fourth side view for illustrating respective processes of the developing method using the developing unit;
• FIG. 12 is a diagram for describing a relationship between a contact angle of a rinse solution and a force applied to collapse patterns when the rinse solution exists between the patterns;
• FIG. 13 is a diagram for describing a reaction mechanism in a hydrophobicizing process in which a first processing solution including TMSDMA hydrophobicizes a surface of a resist pattern;
• FIG. 14 is a cross sectional view illustrating a developing unit in accordance with a first modification example of the first embodiment;
• FIGS. 15A to 15E are schematic diagrams for illustrating a principle of a method for detecting a position of an interface between a rinse solution and an atmosphere;
• FIG. 16 is a schematic diagram illustrating major parts of a developing unit in accordance with a second modification example of the first embodiment;
• FIG. 17 is a flowchart for describing a process sequence of a developing method using the developing unit in accordance with the second modification example of the first embodiment;
• FIG. 18 is a schematic diagram illustrating major parts of a developing unit in accordance with a second embodiment of the present disclosure;
• FIG. 19 is a perspective view illustrating an example vapor supply nozzle provided with a strip-shaped discharge opening;
• FIG. 20 is a flowchart for describing a process sequence of the developing method using the developing unit in accordance with the second embodiment;
• FIGS. 21A to 21D are side views for illustrating respective processes of the developing method using the developing unit in accordance with the second embodiment;
• FIGS. 22A and 22B are plane views for illustrating respective processes of the developing method using the developing unit in accordance with the second embodiment;
• FIG. 23 is a schematic diagram illustrating major parts of a developing unit in accordance with a third embodiment of the present disclosure;
• FIGS. 24A and 24B are enlarged views of a nozzle unit;
• FIG. 25 is a flowchart for describing a process sequence of a developing method using the developing unit in accordance with the third embodiment;
• FIG. 26 is a schematic side view illustrating major parts of a developing unit in accordance with a fourth embodiment of the present disclosure;
• FIG. 27 is a plane view schematically illustrating a vapor supply nozzle; and
• FIG. 28 is a flowchart for describing a process sequence of a developing method using the developing unit in accordance with the fourth embodiment.
BEST MODE FOR CARRYING OUT THE INVENTION
• Hereinafter, embodiments of the present disclosure will be described with reference to the accompanying drawings.
First Embodiment
• Referring toFIGS. 1 to 13, a developing apparatus and a developing method in accordance with a first embodiment of the present disclosure will be explained. The developing apparatus and the developing method in accordance with the first embodiment are related to examples in which a substrate processing apparatus and a substrate processing method in accordance with the present disclosure are applied to a developing apparatus and a developing method, respectively.
• FIGS. 1 to 3 are diagrams illustrating an entire configuration of a coating and developing system including the developing apparatus in accordance with the first embodiment.FIGS. 1 to 3 are a plane view, a front view and a rear view thereof, respectively.
• The coating and developingsystem1 includes acassette station10, aprocessing station11 and aninterface section12 connected as one body. Thecassette station10 loads a plurality of, e.g., 25 sheets of semiconductor wafers W as processing target substrates into a wafer cassette CR of the coating and developing system from the outside and thecassette station10 unloads them from the wafer cassette CR to the outside. Further, thecassette station10 also loads and unloads the wafers W into and from the wafer cassette CR. In theprocessing station11, various processing units for performing single-wafer processes during a coating and developing process are arranged at preset positions in multi levels. Theinterface section14 transfers the wafers W between theprocessing station11 and an exposure apparatus (not shown) adjacent to theprocessing station11.
• As shown inFIG. 1, thecassette station10 may include a cassette mounting table20 and awafer transfer device21. A plurality of, e.g., four wafer cassettes CR may be arranged at positions ofprotrusions20aon the cassette mounting table20 in a row in an X direction such that their respective wafer loading/unloading openings face theprocessing station11. Thewafer transfer device21 is configured to be movable in a cassette arrangement direction (X direction) and also movable in an arrangement direction (Z direction) of the wafers accommodated in the wafer cassette CR. Thewafer transfer device21 is capable of selectively accessing the respective wafer cassettes CR. Further, thewafer transfer device21 is rotatable in a θ direction and is also capable of accessing an alignment unit ALIM and an extension unit EXT included in a third unit set G3 of theprocessing station12 to be described later.
• As depicted inFIG. 1, a mainwafer transfer mechanism22 movable in a vertical direction is provided in a central portion of theprocessing station11, and a single set or multiple sets of processing units are all arranged around the mainwafer transfer mechanism22 in multi levels. In the present embodiment, five unit sets G1 to G5 are arranged in multi levels. Multi-level units of the first unit set G1 and the second unit set G2 are arranged on the front side of the coating and developing system (front side ofFIG. 1). Multi-level units of the third unit set G3 are arranged adjacent to thecassette station10, while multi-level units of the fourth unit set G4 are arranged adjacent to theinterface section12. Further, multi-level units of the fifth unit set G5 are arranged on the rear side of the coating and developing system. The fifth unit set G5 is configured to be movable alongrails25 for the maintenance of the mainwafer transfer mechanism22.
• As depicted inFIG. 3, the mainwafer transfer mechanism22 may include awafer transfer device46 that is configured to be movable up and down in a vertical direction (Z direction). Acylindrical support49 is connected with a rotation shaft of a motor (not shown). Thecylindrical support49 is made to rotate as one body with thewafer transfer device46 about the rotation shaft by a rotational driving force of the motor. Accordingly, thewafer transfer device46 is rotatable in a θ direction. Thewafer transfer device46 may include atransfer arm48.
• As shown inFIG. 2, in the first unit set G1, two spinner type processing units for processing wafers W mounted on spin chucks within cups CP, e.g., a resist coating unit COT and a developing unit DEV in accordance with the first embodiment are stacked in two levels in sequence from the bottom. In the second unit set G2, two spinner type processing units, e.g., a resist coating unit COT and a developing unit DEV are stacked in two levels in sequence from the bottom. Since discharge of a resist solution and maintenance thereof is mechanically troublesome in the resist coating unit COT, it may be desirable to place the resist coating unit COT in a lower level. However, if necessary, the resist coating unit COT may be positioned in an upper level.
• Further, in an empty space below the first unit set G1 and the second unit set G2 in the Z direction, achemical container13 for supplying various processing solutions into the resist coating units COT and the developing units DEV may be provided.
• As illustrated inFIG. 3, in the third unit set G3, oven type processing units for performing preset processes on wafers W mounted on mounting tables, e.g., a cooling unit COL, an adhesion unit AD, an alignment unit ALIM, an extension unit EXT, prebaking units PAB and post exposure baking units PEB are stacked in sequence from the bottom. Further, in the fourth unit set G4, oven type processing units, e.g., a cooling unit COL, an extension/cooling unit EXTCOL, an extension unit EXT, a cooling unit COL, prebaking units PAB and post exposure baking units PEB are stacked in sequence from the bottom. Further, a post baking unit for heating the wafers W after a developing process may be provided.
• In the above-described configuration, the cooling units COL and the extension/cooling unit EXTCOL having low processing temperatures are arranged in lower levels, while the prebaking units PAB and the post exposure baking units PEB having high processing temperatures are arranged in upper levels. With this vertical arrangement, thermal interference between the units can be reduced. However, these units may be randomly arranged in multi levels.
• Theinterface section12 may have the same size as that of theprocessing station11 in a depth direction but may have a smaller size than that of theprocessing station11 in a widthwise direction. A portable pickup cassette PU and a stationary buffer cassette BR are arranged in two levels on the front side of theinterface section12, and aperipheral exposure device23 is provided on the rear side of theinterface section12. Further, awafer transfer device24 is installed in a central portion of theinterface section12. Thewafer transfer device24 is movable in X and Z directions and is capable of accessing the two cassettes PU and BR and theperipheral exposure device23. Further, thewafer transfer device24 is rotatable in a θ direction and is capable of accessing the extension unit EXT of the fourth unit set G4 in theprocessing station11 as well as a wafer transfer table (not shown) of the exposure apparatus (not shown) adjacent to theinterface section12.
• FIGS. 4 and 5 are a plane view and a cross sectional view of a developing unit in accordance with the first embodiment. In a central portion of a developing unit DEV, an annular cup CP is provided within aprocessing chamber25 of which atmosphere is capable of being controlled to be different from an external atmosphere. In order to prevent leakage of vapor of a first processing solution to the outside, as will be described later, the inside of theprocessing chamber25 may be adjustable to a negative pressure. Further, the cup CP is configured to allow thetransfer arm48 of thewafer transfer device46 to be moved back and forth. Aspin chuck52 for horizontally holding the wafer W thereon is provided within the cup CP. Thespin chuck52 is rotated by drivingmotor54 while the wafer W is held on thespin chunk52 by vacuum attraction. The drivingmotor54 is provided in anopening50aformed in aunit bottom plate50 so as to be movable up and down and is coupled to anelevation driving unit60 composed of an air cylinder and anelevation guiding unit62 via a cap-shapedflange58 made of aluminum. By this elevating mechanism, the wafer W can be transferred from and to the mainwafer transfer mechanism22.
• Further, thespin chuck52 serves as a substrate holder in accordance with the present disclosure, and the drivingmotor54 serves as a rotating unit and a rinse solution removing unit in accordance with the present disclosure.
• As illustrated inFIG. 5, a developingsolution nozzle36 for supplying a developing solution onto a surface of the wafer W accommodated in the cup CP from above the wafer W is fixed at a leading end of anozzle scan arm37. Asupply pipe31ais connected with the developingsolution nozzle36, and the developing solution is supplied through thesupply pipe31aby a developingsolution supply mechanism31. The developingsolution nozzle36 has an elongated shape and is provided with, e.g., a multiple number of hole-shaped or slit-shaped supply openings through which the developing solution is supplied. Thenozzle scan arm37 is fixed at an upper end of a vertical supportingmember40 which is configured to be horizontally movable in one direction (Y direction) on a guide rail38 installed on theunit bottom plate40. Thenozzle scan arm37 is configured to be movable in a Y direction as one body with the vertical supportingmember40 by a non-illustrated Y-direction driving mechanism. Furthermore, thenozzle scan arm37 is also configured to be movable in a Z direction along thevertical support member40, so that a distance between the developingsolution nozzle36 and the wafer W held on thespin chuck52 can be adjusted.
• Further, a rinsenozzle15, held by anozzle holder27, for supplying a rinse solution onto the surface of the wafer W is installed so as to be movable in the Y direction along the guide rail38 by anozzle scan arm17 and a vertical supportingmember26, as in the case of the developingsolution nozzle36. Asupply pipe32ais connected with the rinsenozzle15, and the rinse solution is supplied from a rinsesolution supply mechanism32 through thesupply pipe32a. Here, the rinse solution may be, for example, pure water. Thenozzle scan arm17 is also configured to be movable along the vertical supportingmember26, so that a distance between the rinsenozzle15 and the wafer W held on thespin chuck52 can be adjusted.
• Further, the rinsenozzle15 serves as a rinse solution supply unit in accordance with the present disclosure.
• Adjacent to the cup CP, avapor supply nozzle16, held by anozzle holder28, is fixed at a leading end of anozzle scan arm18, and thevapor supply nozzle16 supplies vapor of a first processing solution including a hydrophobicizing agent for hydrophobicizing a surface of a resistpattern29 on the wafer W. Thenozzle scan arm18 is rotatable about amotor19 in a θ direction by being driven by themotor19. Asupply pipe33ais connected with thevapor supply nozzle16, and the vapor of the first processing solution is supplied from avapor supply mechanism33 through thesupply pipe33a.
• Further, thevapor supply nozzle16 and themotor19 serves as a vapor supply unit and a moving unit in accordance with the present disclosure, respectively.
• Aliquid drain pipe57 for draining the developing solution and the rinse solution supplied onto the wafer is provided in a bottom of the cup CP, and the developing solution and the rinse solution are drained to the non-illustrated outside of the system. Further, also installed in the bottom of the cup CP is agas exhaust pipe59 for exhausting an atmosphere within the cup CP such as mist generated by the supply of the developing solution or the processing solution. Typically, during the operation, the atmosphere within the cup CP continues to be exhausted by avacuum pump51.
• Moreover, atemperature sensor64 for measuring a temperature of the cup CP and atemperature control heater65 for controlling the temperature of the cup CP are installed at the cup CP. Usually, thetemperature control heater65 controls the temperature of the entire cup CP to be a preset value, e.g., about 23° C. or thereabout.
• In the same way, atemperature sensor66 for measuring a temperature of thegas exhaust pipe59 and atemperature control heater68 for controlling the temperature of thegas exhaust pipe59 are installed at thegas exhaust pipe59, and atemperature sensor67 for measuring a temperature of theliquid drain pipe57 and atemperature control heater69 for controlling the temperature of theliquid drain pipe57 are installed at theliquid drain pipe57.
• The developingsolution supply mechanism31, the rinsesolution supply mechanism32 and thevapor supply mechanism33 supply the developing solution, the rinse solution and the vapor of the first processing solution to the developingsolution nozzle36, the rinsenozzle15 and thevapor supply nozzle16, respectively, in response to instructions of acontroller30. Further, thecontroller30 controls timing for the supply of the developing solution, the rinse solution and the vapor of the first processing solution and sends an instruction to amotor controller34 for controlling a rotation speed of the drivingmotor54 to thereby control an overall process of the developing unit.
• Thecontroller30 may have a non-illustrated storage composed of a computer readable storage medium (recording medium) that stores a program for executing each process of a developing method in the coating and developing system. The storage medium may be a hard disk or a semiconductor memory. Alternatively, a control program may be appropriately transmitted from another apparatus through, e.g., a dedicated line.
• Further, by way of example, when the temperatures of the cup CP, thegas exhaust pipe59 and theliquid drain pipe57 respectively measured by thetemperature sensors64,66 and67 fall out of preset ranges, thecontroller30 determines that abnormality has occurred, and controls analarm device45 to give an alarm based on the abnormality determination. Thealarm device45 may be, but not limited to, a buzzer, an alarm lamp, an alarm mark on a manipulation display, or the like.
• Now, a series of processes performed by the above-described coating and developingsystem1 will be explained.
• First, in thecassette station10, thewafer transfer device21 accesses the wafer cassette CR, in which unprocessed wafers W are accommodated, on the cassette mounting table20 and takes out one of the unprocessed wafers W from the wafer cassette CR. The wafer W taken from the wafer cassette CR is then transferred into the alignment unit ALIM, and position alignment of the wafer W is performed by the alignment unit ALIM. Thereafter, by the mainwafer transfer mechanism22, the wafer W is transferred into the adhesion unit AD for performing a hydrophobicizing process and then is transferred into the cooling unit COL for performing a cooling process. Afterward, the wafer W is transferred into the resist coating unit COT for performing a resist coating process; the wafer W is transferred into the prebaking unit PAB for performing a heating process; and then the wafer W is transferred into the cooling unit COL for performing a cooling process. Thereafter, the wafer W is transferred by thewafer transfer device24 into the non-illustrated exposure apparatus via theinterface section12, and an exposure process is performed in the exposure apparatus. After the exposure process of the wafer W is completed, the wafer W is transferred into the post exposure baking unit PEB for performing a heating process and then is transferred into the cooling unit COL for performing a cooling process. Subsequently, the wafer W is transferred into the developing unit DEV, and a developing process is performed by the developing unit DEV. After the developing process is finished, a heating process (post baking) may be performed. Then, the wafer W is transferred into the cooling unit COL, and a cooling process is performed by the cooling unit COL and the wafer W is then returned back into the wafer cassette CR by the extension unit EXT.
• FIG. 6 is a diagram schematically illustrating major parts of the developing unit in accordance with the embodiment of the present disclosure. Further, inFIG. 6, elaboration of parts already described inFIGS. 4 and 5 will be omitted.
• Further,FIG. 6 schematically illustrates positions of the respective nozzles when a rinse solution removing process is performed after the completion of a developing solution supply process and a rinse solution supply process to be described later with reference toFIG. 7. That is, the developingsolution nozzle36 is located outside the cup CP, and the rinsenozzle15 is located at a position slightly deviated from an approximate center of the wafer W toward a periphery of the wafer W. Thevapor supply nozzle16 is placed at a position above the approximate center of the wafer W.
• Thevapor supply mechanism33 includes avapor generating tank71 that generatesvapor44 by vaporizing afirst processing solution43 including a hydrophobicizing agent. Thevapor generating tank71 stores thefirst processing solution43 therein. Thevapor generating tank71 is connected with one end of thesupply pipe33afor supplying thevapor44 of the first processing solution. As stated above, the other end of thesupply pipe33ais connected with thevapor supply nozzle16 via avalve72 configured to be opened and closed by thecontroller30.
• Connected to thevapor generating tank71 is one end of a carriergas supply pipe73 for supplying a carrier gas such as a N₂gas. The other end of the carriergas supply pipe73 is connected with a carriergas supply source75 via avalve74 configured to be opened and closed by thecontroller30. As the carrier gas supplied into thevapor generating tank71 from the carriergas supply source75 pressurizes the inside of thevapor generating tank71, thevapor44 generated in thevapor generating tank71 is supplied into thevapor supply nozzle16 through thesupply pipe33a. If thefirst processing solution43 includes TMSDMA as will be described later, thefirst processing solution43 may readily react with moisture in the atmosphere. For this reason, by using the carrier gas such as the N₂gas, thefirst processing solution43 and thevapor44 of the first processing solution may be prevented from reacting with the moisture in the atmosphere.
• Furthermore, on a part of thesupply pipe33a, thesupply pipe33ais connected with one end of a dilutiongas supply pipe76 for supplying a dilution gas such as a N₂gas. The other end of the dilutiongas supply pipe76 is connected with a dilutiongas supply source78 via avalve77 configured to be opened and closed by thecontroller30.
• In thevapor supply mechanism33 configured as described above, thevalve74 is opened under the control of thecontroller30, and the carrier gas is supplied from the carriergas supply source75 into thevapor generating tank71 through the carriergas supply pipe73 at a certain flow rate. Then, thevalve72 is opened, and thevapor44 of the first processing solution vaporized within thevapor generating tank71 is supplied into thevapor supply nozzle16 through thesupply pipe33aalong with the carrier gas. Here, thevapor44 of the first processing solution may be supplied into thevapor supply nozzle16 after thevapor44 is diluted with the dilution gas introduced into thesupply pipe33afrom the dilutiongas supply source78 via thevalve77 and the dilutiongas supply pipe76. On the contrary, in order to stop the supply of thevapor44 of the first processing solution into thevapor supply nozzle16, thevalve72 of thesupply pipe33aand thevalve77 of the dilutiongas supply pipe76 are closed, and thevalve74 is also closed to thereby stop the supply of the carrier gas from the carriergas supply source75.
• In addition, a non-illustrated supply source for continuously supplying thefirst processing solution43 including the hydrophobicizing agent may be connected with thevapor generating tank71 via a non-illustrated supply pipe. Further, it may also be possible to install a non-illustrated liquid surface sensor that detects a maximum and minimum height of a surface of the storedfirst processing solution43 and sends a detection signal to thecontroller30.
• Here, the hydrophobicizing agent that hydrophobicizes the resist pattern may not be particularly limited. By way of example, a molecular compound having a silyl group of (CH₃)₃Si may be used as the hydrophobicizing agent. One example of such a silyl group may be TMSDMA (Trimethylsilyldimethylamine).
• Furthermore, in the present embodiment, a mixture of a hydrophobicizing agent and an organic solvent for diluting the hydrophobicizing agent may be used as the first processing solution instead of the hydrophobicizing agent itself. A fluorine-containing organic solvent for diluting the hydrophobicizing agent may be, but not limited to, a hydrofluoroether (HFE)-based solvent (methylperfluoroisobutylether, methylperfluorobutylether, or a mixture thereof) having higher volatility than pure water. Further, xylene, hexamethyldisilazane or the like may also be used. The HFE-based solvent does not dissolve a resist and thus can be supplied onto the resist.
• Further, thevapor generating tank71 may include a temperature controller composed of, e.g., a heating device such as a heater or a cooling device such as a Peltier element capable of controlling an internal temperature of thevapor generating tank71 so as to generate an optimum amount ofvapor44 depending on the hydrophobicizing agent included in thefirst processing solution43. When TMSDMA or TMSDMA diluted with HFE is used as the hydrophobicizing agent, the temperature controller may control the internal temperature of thevapor generating tank71 to be substantially the same as a room temperature.
• Now, referring toFIGS. 7 to 11, a developing method using the developing unit will be described.FIG. 7 is a flowchart for describing a process sequence, andFIGS. 8 to 11A are side views for illustrating respective processes.
• As depicted inFIG. 7, the developing method in accordance with the present embodiment may include a developing solution supply process (step S11), a rinse solution supply process (step S12), a film thickness adjusting process (step S13), a rinse solution removing process (steps S14 to S16) and a drying process (step S17). The rinse solution removing process may include a first removing process (step S14), a second removing process (step S15) and a third removing process (step S16).
• Furthermore, example processing recipes for the developing method shown inFIG. 7 are specified in Table 1.

• TABLE 1
  				Nozzle position
  				(mm) with respect
  Step		Time	Rotation	to substrate
  No.	Process name	(sec)	speed (rpm)	center	Liquid chemical

  S12	Rinse solution supply	2~15	0~1200	0	Rinse solution
  	process
  S13	Film thickness adjusting	3	1000	—	—
  	process
  S14
  	1stremoving process	3	1000	0	Vapor of first
  					processing
  					solution
  S15	2ndremoving process	3	100	25	Vapor of first
  					processing
  					solution
  S16	3rdremovingprocess	1	1000	150	Vapor of first
  					processing
  					solution
  S17	Drying process		15	2000	—	—

• From the left of Table 1, columns represent a step number, a process name, time, a rotation speed (rpm), a nozzle position (mm) with respect to a substrate center and a kind of a liquid chemical supplied in each step in sequence. Further, the nozzle position (mm) with respect to the substrate center indicates a position when a wafer having a diameter of about 12 inches is processed.
• First, the developing solution supply process (step S11) is performed. In this developing solution supply process (step S11), a developingsolution41 is supplied onto the wafer W, and a resistpattern29 is developed.
• Thespin chuck52 is elevated upward and receives the wafer W from the mainwafer transfer mechanism22. Then, thespin chuck51 is lowered, and the wafer W having the resistpattern29 formed thereon is accommodated in the cup CP. Thereafter, as illustrated inFIG. 8A, the developingsolution nozzle36 is moved over the wafer W while supplying the developingsolution41 onto the wafer W. After the supply of the developingsolution41 is completed, the wafer W is left in that state for, e.g., about 60 seconds, so that the developing process progresses. Here, in order to achieve high throughput, the developingsolution41 may be supplied while the wafer W is being rotated. In such a case, the developingsolution41 may be diffused by rotating the wafer W at a preset rotation speed. Then, the wafer W is maintained in that state for, e.g., about 60 seconds, so that the developing process progresses.
• Subsequently, the rinse solution supply process (step S12) is carried out. In the rinse solution supply process (step S12), a rinsesolution42 is supplied onto the wafer W of which the resistpattern29 is developed, so that the developingsolution41 is removed from the wafer W.
• As shown inFIG. 8B, the developingsolution nozzle36 is moved out of the cup, and the rinsenozzle15 is moved to a position above an approximate center of the wafer W. Then, as illustrated inFIG. 8C, the rinsesolution42 is supplied while the wafer W is being rotated, so that the developingsolution41 is washed away. Here, since the supply of the rinsesolution42 is performed while the wafer W is being rotated, the surface of the wafer W can be rinsed by the rinsesolution42 while the developingsolution41 is scattered away.
• A liquid film (pure water puddle) of the rinse solution (pure water)42 is formed on the surface of the wafer W. In order to prevent atop surface29aof the resistpattern29 to be described later with reference toFIG. 12 from being exposed out of the rinsesolution42, the rotation speed of the wafer W is set to be relatively low, e.g., about 0 rpm to about 1200 rpm and, more desirably, about 500 rpm. If thetop surface29aof the resistpattern29 is exposed out of the rinsesolution42, pattern collapse may be caused due to a surface tension of the rinsesolution42. Thus, by rotating the wafer W at a relatively low speed of about 0 rpm to about 1200 rpm, a flow velocity of the rinsesolution42 on the wafer W can be reduced, so that collapse of the resistpattern29 can be avoided when the developingsolution41 is removed. Alternatively, the wafer W may be rotated in multiple steps. For example, the wafer W may be rotated at about 100 rpm for about 2 seconds, then rotated at about 1200 rpm for about 3 seconds and then rotated at about 500 rpm for about 10 seconds.
• Subsequently, the film thickness adjusting process (step S13) is performed. In the film thickness adjusting process (step S13), the supply of the rinsesolution42 is stopped, and a part of the rinsesolution42 is scattered away by rotating the wafer W, and, thus, a thickness of the liquid film of the rinsesolution42 is adjusted.
• As depicted inFIG. 8d, the thickness of the liquid film (pure water puddle) of the rinse solution (pure water)42 is reduced by increasing the rotation speed of the wafer W. By reducing the thickness of the liquid film (pure water puddle) of the rinse solution (pure water)42, a part of the rinse solution may be repelled and a part of the surface of the wafer W would be exposed when thevapor44 of the first processing solution is supplied during the subsequent rinse solution removing process (steps S14 to S16). Thus, an interface B between the rinsesolution42 and an atmosphere (vapor44 of the first processing solution) can be formed on the surface of the wafer W. The rotation speed of the wafer W may be set to be, e.g., about 1000 rpm.
• Thereafter, the rinse solution removing process (steps S14 to S16) is carried out. In the rinse solution removing process (step S14 to step S16), the wafer W is rotated while thevapor44 of the first processing solution is supplied onto the wafer W, so that the rinsesolution42 is scattered (spun) and removed away. Further, the rinse solution removing process (step S14 to step S16) includes the first removing process (step S14), the second removing process (step S15) and the third removing process (step S16), as mentioned above.
• Below, there will be discussed an example in which the rinsesolution42 is scattered and removed by rotating the wafer W while thevapor44 of the first processing solution is being supplied onto the wafer W. However, it may be also possible to rotate the wafer W after thevapor44 of the first processing solution is supplied. In such a case, although the rotation of the wafer W is not performed while thevapor44 of the first processing solution is being supplied, the wafer W may be rotated in an atmosphere including thevapor44 of the first processing solution, so that the rinsesolution42 is scattered and removed away from the wafer W.
• First, the first removing process (step S14) is carried out. In the first removing process (step S14), the wafer W is rotated while thevapor44 of the first processing solution is being supplied onto the approximate center of the wafer W, so that the rinsesolution42 is scattered and removed away.
• As illustrated inFIG. 9A, the rinsenozzle15 is moved out of the cup CP, and thevapor supply nozzle16 is moved to a position above the approximate center of the wafer W. Then, as illustrated inFIG. 9B, while supplying thevapor44 of the first processing solution from thevapor supply nozzle16 located at a position above the approximate center of the wafer W, the wafer W is rotated by the drivingmotor54 at a first rotation speed R1 for a first time T1.
• When thevapor supply nozzle16 is located at the ‘position above the approximate center of the wafer W’, the position of thevapor supply nozzle16 may be referred to as a first position P1. By way of example, the first position P1 may be, e.g., about 0 mm to about 5 mm and, more desirably, about 0 mm.
• The first rotation speed R1 may be adjusted so as to reduce the thickness of the liquid film (pure water puddle) of the rinse solution (pure water)42, as in the film thickness adjusting process (step S13). By way of example, the first rotation speed R1 may be set to be about 500 rpm to about 1500 rpm and, more particularly, to about 1000 rpm.
• The first time T1 may be substantially the same as a time period taken until the interface between the rinsesolution42 and the atmosphere (vapor44 of the first processing solution) is formed on the surface of the wafer W after the supply of thevapor44 of the first processing solution is begun, as will be described below. Further, the first time T1 may be a time period during which the resistpattern29 is not dissolved. Since the TMSDMA used as the hydrophobicizing agent has a property of dissolving the resist, it is necessary that the first time T1 may be set to be, e.g., about 0.5 to about 5 seconds and, more desirably, about 3 seconds.
• As illustrated inFIG. 9c, if thevapor44 of the first processing solution is supplied and, thus, a concentration, i.e., a pressure of thevapor44 of the first processing solution increases at the approximate center of the wafer W, the rinsesolution42 may be moved to a periphery of the wafer W in which the concentration, i.e., the pressure of thevapor44 of the first processing solution is low. As a result, the liquid film of the rinsesolution42 may be recessed at the approximate center of the wafer W, so that a thickness of the liquid film at the approximate center of the wafer W would be reduced, whereas the thickness of the liquid film at the periphery of the wafer W would be increased. Then, if thevapor44 of the first processing solution continues to be supplied and the rinsesolution42 is scattered away by the rotation of the wafer W, a part of the rinsesolution42 may be repelled on the approximate center of the wafer W and be removed away, as illustrated inFIG. 9D. As a consequent, a part of the surface of the wafer W may be exposed, and the interface B between the rinsesolution42 and the atmosphere (vapor44 of the first processing solution) is formed on the surface of the wafer W.
• If the concentration of thevapor44 of the first processing solution increases at the approximate center of the wafer W, thevapor44 of the first processing solution and the rinsesolution42 may be mixed with each other, resulting in reduction of the surface tension of the rinsesolution42. Furthermore, if the concentration of thevapor44 of thefirst processing solution44 increases at the approximate center of the wafer W, thevapor44 of the first processing solution and the rinsesolution42 may be mixed with each other, and the mixture may reach the surface of the resistpattern29 on the wafer W and may hydrophobicize the surface of the resistpattern29.
• Further, inFIGS. 9B to 10D, thevapor44 of the first processing solution supplied from thevapor supply nozzle17 is shown to have a certain area for the purpose of illustration. Since, however, thevapor44 of the first processing solution diffuses as a gas, there exists no clear boundary.
• Subsequently, the second removing process (step S15) is performed. In the second removing process (step S15), the rinsesolution42 is scattered away by rotating the wafer W while slightly shifting the position, where thevapor44 of the first processing solution is supplied onto the wafer W, toward the periphery of the wafer W from the approximate center thereof.
• As illustrated inFIG. 10A, while the position of thevapor supply nozzle16 with respect to the approximate center of the wafer W is being shifted to a position slightly deviated toward the periphery of the wafer W from the approximate center of the wafer W by themotor19 for a second time T2, the wafer W is rotated at a second rotation speed R2 by the drivingmotor54.
• When thevapor supply nozzle16 is located at the ‘position slightly deviated toward the periphery of the wafer W’ from the center of the wafer W, the position of thevapor supply nozzle16 may be referred to as a second position P2. By way of example, the second position P2 may be, e.g., about 5 mm to about 50 mm and, more desirably, about 25 mm.
• The second rotation speed R2 may be adjusted to reduce a speed for moving the interface B between the rinsesolution42 and the atmosphere (vapor44 of the first processing solution) toward the periphery of the wafer W, as will be described later. Desirably, the second rotation speed R2 may be lower than the first rotation speed R1, and the second rotation speed R2 may be set to be about 0 rpm to about 500 rpm and, more desirably, about 100 rpm.
• The second time T2 may be substantially the same as a time period taken until the interface B between the rinsesolution42 and the atmosphere (vapor44 of the first processing solution) starts to be moved instantly toward the periphery of the wafer W after the interface B is formed, as will be described below. Further, the second time T2 may be a time period during which the resistpattern29 is not dissolved. By way of example, the second time T2 may be set to be, e.g., about 0.5 to about 10 seconds and, more desirably, about 3 seconds.
• In the first removing process (step S14), as a part of the rinsesolution42 is repelled on the approximate center of the wafer W, a part of the surface of the wafer W may be exposed, and the interface B between the rinsesolution42 and the atmosphere (vapor44 of the first processing solution) may be formed on the surface of the wafer W. In this state, if the wafer W is rotated at the same speed, the rinsesolution42 may be scattered away, so that the interface B between the rinsesolution42 and the atmosphere (vapor44 of the first processing solution) may be moved toward the periphery of the wafer W instantly. If, however, the interface B between the rinsesolution42 and the atmosphere (vapor44 of the first processing solution) is moved toward the periphery of the wafer W too fast, the surface tension of the rinsesolution42 may not be reduced, or the surface of the resistpattern29 may not be hydrophobicized by thevapor44 of the first processing solution, resulting in collapse of the resistpattern29. Accordingly, in the second removing process (step S15), by shifting the position for supplying thevapor44 of the first processing solution slightly toward the periphery of the wafer W from the approximate center thereof, the surface tension of the rinsesolution42 may be reduced at the periphery of the wafer W or the surface of the resistpattern29 may be hydrophobicized thereat. Further, by decreasing the rotation speed of the wafer W, the speed at which the interface B between the rinsesolution42 and the atmosphere (vapor44 of the first processing solution) is moved toward the periphery of the wafer W can also be decreased. Then, instant shift of the interface B between the rinsesolution42 and the atmosphere (vapor44 of the first processing solution) toward the periphery of the wafer W is awaited.
• In accordance with the first embodiment, in the first removing process (step S14), thevapor supply nozzle16 is shifted toward the periphery of the wafer W as illustrated inFIG. 10A after the interface B between the rinsesolution42 and the atmosphere (vapor44 of the first processing solution) is formed on the approximate center of the wafer W as depicted inFIG. 9D. However, the shift of thevapor supply nozzle16 may be started at the same time or slightly before the interface B between the rinsesolution42 and the atmosphere (vapor44 of the first processing solution) is formed on the approximate center of the wafer W. In such a case, in the first removing process (step S14), the rinsesolution42 may be scattered away by rotating the wafer W while supplying thevapor44 of the first processing solution onto the approximate center of the wafer W in a state that the surface of the approximate center of the wafer W is yet to be completely dried. Furthermore, in the second removing process (step S15), in a state that the surface of the approximate center of the wafer W is yet to be completely dried, the rinsesolution42 may be scattered away by rotating the wafer W while slightly shifting the position for supplying thevapor44 of the first processing solution toward the periphery of the wafer W from the approximate center thereof. In such a case, this state is not exactly the same as the state shown inFIG. 9D.
• Subsequently, the third removing process (step S16) is performed. In the third removing process (step S16), the rinsesolution42 is scattered and removed by rotating the wafer W while instantly shifting the position where thevapor44 of the first processing solution is supplied to an approximate edge of the wafer W.
• As illustrated inFIGS. 10A to 10D, while the position of thevapor supply nozzle16 with respect to the center of the wafer W is instantly shifted to the approximate edge of the wafer W for a third time T3 by themotor19, the wafer W is rotated at a third rotation speed R3 by the drivingmotor54.
• When thevapor supply nozzle16 is located at ‘the approximate edge of the wafer W’, the position of thevapor supply nozzle16 may be referred to as a third position P3. By way of example, the third position P3 may be set to be about 100 mm to about 200 mm and, more particularly, about 150 mm.
• The third rotation speed R3 may be adjusted so as to allow the interface B between the rinsesolution42 and the atmosphere (vapor44 of the first processing solution) to be instantly moved to the approximate edge of the wafer W, as will be described later. Desirably, the third rotation speed R may be higher than the second rotation speed R2. By way of example, the third rotation speed R3 may be in the range of about 500 rpm to about 1500 rpm and, more desirably, the third rotation speed R3 may be about 1000 rpm.
• The third time T3 may be substantially the same as a time period taken until the interface B between the rinsesolution42 and the atmosphere (vapor44 of the first processing solution) is instantly moved to the approximate edge of the wafer W from the approximate center of the wafer W, as will be described below. Further, the third time T3 may be a time period during which the resistpattern29 is not dissolved. By way of example, the third time T3 may be set to be, e.g., about 1 second to about 10 seconds and, more desirably, about 1 second.
• By increasing the rotation speed of the wafer W, the interface B between the rinsesolution42 and the atmosphere (vapor44 of the first processing solution) is instantly moved to the periphery of the wafer W. Further, by instantly moving thevapor supply nozzle16 to the approximate edge of the wafer W, the position where thevapor44 of the first processing solution is supplied to the wafer W can be moved along with the interface B between the rinsesolution42 and the atmosphere (vapor44 of the first processing solution). That is, by rotating thespin chuck52 by the drivingmotor54 while moving the position, where thevapor44 of the first processing solution is supplied, at a speed corresponding to a speed at which the rinsesolution42 is scattered and moved by themotor19, the rinsesolution42 can be scattered (spun) and removed.
• Further, in the first embodiment, the rinse solution removing process is described to include steps S14 to S16. However, the rinsesolution42 may be removed by performing only step S14 without performing steps S15 and S16. That is, the rinsesolution42 may be scattered and removed by rotating the wafer W while supplying thevapor44 of the first processing solution to the approximate center of the wafer W without moving thevapor supply nozzle16 from the approximate center of the wafer W.
• Then, the drying process (step S17) is performed. In the drying process (step S17), the wafer W is rotated at a preset rotation speed and thus is dried.
• As illustrated inFIG. 11, the wafer W is rotated by the drivingmotor54 at a high rotation speed of, e.g., about 1500 rpm to about 2500 rpm, more desirably, about 2000 rpm, so that the surface of the wafer W is sufficiently dried.
• Furthermore, in the first embodiment, the rinsesolution42 may not be supplied again for cleaning after the rinse solution removing process (steps S14 to S16). However, depending on conditions such as the kind of the resist or the rinsesolution42, the shape of the resistpattern29 on the wafer W, and the like, a rinse solution supply process may be performed again between the rinse solution removing process and the drying process (step S17). In such a case, since the surface of the resistpattern29 is already hydrophobicized as a result of performing the rinse solution removing process (steps S14 to S16), the resistpattern29 may not collapse even if the rinse solution supply process is performed again.
• Below, an effect of preventing collapse of a resist pattern by using the vapor of the first processing solution and an effect of reducing an amount of usage of the first processing solution in accordance with the first embodiment will be discussed. Further, in the following description, a resist pattern may be simply referred to as a ‘pattern’.
• FIG. 12 provides a diagram for describing a relationship between a contact angle of a rinse solution and a force for collapsing patterns when the rinse solution exists between the patterns. In the course of drying the rinsesolution42 after rinsing a gap between two resistpatterns29 by the rinsesolution42, one side of the resistpattern29 may be in contact with the rinsesolution42 while the other side thereof is dried and is in contact with air, as depicted inFIG. 12. In such a state, since the one side of the resistpattern29 is pressed by the rinsesolution42 while the other side is pressed by the air, a force for collapsing the resistpatterns29 may be exerted due to such a pressure difference. The force F for collapsing the patterns may be represented by the following Eq. (1).
• $\begin{array}{cc}\left[\mathrm{Eq}.1\right]& \\ F=\frac{2\gamma \cos \theta }{D}\mathrm{HL}& \left(1\right)\end{array}$
• Here, γ is a surface tension of the rinse solution; θ, a contact angle of the rinse solution with respect to a pattern; D, a distance between patterns; H, a height of the pattern; and L, a length of the pattern. The force F for collapsing the pattern generates a moment for bending the pattern. If the width of the pattern is W1, a maximum stress σ_maxapplied to the pattern may be represented by the following Eq. (2).
• $\begin{array}{cc}\left[\mathrm{Eq}.2\right]& \\ {\sigma }_{\mathrm{MAX}}=\frac{6\gamma \cos \theta }{D}{\left(\frac{H}{W1}\right)}^2& \left(2\right)\end{array}$
• Accordingly, when σ_Maxexceeds a collapse stress σ_CRT(σ_MAX>σ_CRT) of the pattern, the pattern may be collapsed. Based on these equations, some methods to prevent collapse of the pattern may be considered: (1) enlarging the distance D between patterns; (2) reducing an aspect ratio of the pattern by decreasing the height H of the pattern or by increasing the width W1 of the pattern; (3) reducing the surface tension γ of the rinsesolution42; and (4) reducing cos θ by increasing the contact angle θ of the rinsesolution42 with respect to the pattern.
• Among the mentioned methods, in the developing method in accordance with the first embodiment, the maximum stress σ_MAXapplied to the pattern may be reduced to prevent the pattern collapse by (3) decreasing the surface tension γ of the rinsesolution42 or by (4) increasing the contact angle θ.
• FIG. 13 is a diagram for describing a reaction mechanism of a hydrophobicizing process for hydrophobicizing a surface of a resist pattern by a first processing solution including TMSDMA. TMSDMA included in the processing solution may have a silyl group of (CH₃)₃Si in its molecule. Meanwhile, resist has an OH group in its polymer structure. The silyl group of the TMSDMA is substituted with H of the OH group of the resist on the surface of the resist pattern. The OH group is hydrophilic, whereas a group formed by substituting the H of the OH group with the silyl group is hydrophobic. Accordingly, the surface of the resist pattern may be hydrophobicized by the hydrophobic group formed on the surface of the resist pattern.
• The contact angle θ of the rinsesolution42 with respect to the resistpattern29 shown inFIG. 12 was measured after the completion of the rinse solution removing process for removing the rinsesolution42 while supplying thevapor44 of the first processing solution, and the contact angle θ was found to range from about 85° to about 95°. Accordingly, when the rinsesolution42 is removed from between the patterns, pattern collapse may not be caused. Furthermore, once the contact angle θ of the rinsesolution42 with respect to the resistpattern29 is increased, i.e., after the hydrophobicization of the surface of the resistpattern29 is performed, such a large contact angle can also be achieved for the rinsesolution42 composed of pure water.
• In the present embodiment, a first processing solution composed of TMSDMA diluted with HFE may be used instead of TMSDMA. Even if the TMSDMA is diluted with HFE, it is also possible to achieve the effect of hydrophobicizing the surface of the resist pattern by the silyl group in the TMSDMA. Meanwhile, since the HFE has fluorine, the surface of the resistpattern29 may be coated with fluorine. Accordingly, even in case the first processing solution composed of the TMSDMA diluted with the HFE is used, a contact angle in the above-specified high angular range can also be obtained.
• Further, a hydrophobic group is formed on the surface of the resistpattern29 by the silyl group of the TMSDMA, so that the surface of the resistpattern29 is hydrophobicized. By way of example, after the hydrophobic group is formed, an additional reaction may be made by performing heat treatment such as post baking, and, thus, the surface of the resistpattern29 may be chemically stabilized, as in the case of so-called silylation. Accordingly, since the surface of the resistpattern29 has resistance against etchant used in a subsequent process of etching the wafer W by using the resistpattern29 as a mask, selectivity, i.e., a ratio of an etching rate of the wafer W to an etching rate of the resistpattern29 can be improved, and formation of finer patterns or formation of patterns having a higher aspect ratio can be carried out accurately.
• Now, investigation result of a pattern collapse preventing effect by the developing method in accordance with the first embodiment will be described with reference to Table 2.
Experimental Example 1
• In an experimental example 1, as for wafers on which resist was coated and pattern exposure was performed while varying a dose amount during the exposure in the range of about 27 ml to about 32 ml, development of resist patterns formed on the wafers was carried out by performing steps S11 to S17 as described inFIG. 7. Each of steps S13 to S17 was performed according to example processing recipes specified in Table 1. In steps S14 to S16, a vapor of a first processing solution made of 100% of TMSDMA was used. The resist pattern was formed to have a line width of about 120 nm, a space width of about 120 nm (a pitch of about 240 nm) and a height of about 380 nm. Then, by using a SEM (Scanning Electron Microscope), it was observed whether collapse of pattern had occurred in the patterns formed by using the respective dose amounts. The result is depicted in Table 2.
Comparative Example 1
• In a comparative example 1, as for wafers on which the same pattern exposure as in the experiment example 1 was performed, development of resist patterns having the same shapes as those in the experimental example was conducted by performing steps S11 to S13 and step S17 inFIG. 7 while omitting steps S14 to S16. In this example, however, a rinse solution composed of HFE was used in step S13 instead of using pure water. Further, as in the experimental example 1, it was observed whether collapse of pattern had occurred in the patterns formed by using respective dose amounts. The result is depicted in Table 2.
Comparative Example 2
• In a comparative example 2, as for wafers on which the same pattern exposure as in the experiment example 1 was performed, development of resist patterns having the same shapes as those in the experimental example was conducted by performing steps S11 to S13 and step S17 inFIG. 7 while omitting steps S14 to S16. The comparative example 2 corresponds to a conventional developing process in which rinse is performed by using pure water. Further, as in the experimental example 1, it was observed whether collapse of pattern had occurred in the patterns formed by using respective dose amounts. The result is depicted in Table 2.

• 	TABLE 2
  	Dose amount (mJ)
  	during exposure

  Example	27	28	29	30	31	32
  Experimental example 1	∘	∘	∘	∘	∘	∘
  (Removing rinse solution in
  atmosphere of vapor of TMSDMA)
  Comparative example 1	∘	∘	x	∘	x	x
  (Removing rinse solution after
  substituting the rinse solution with HFE)
  Comparative example 2	∘	∘	x	x	x	x
  (Removing rinse solution (pure water))
  (∘: no pattern collapse has occurred, x: pattern collapse has occurred)

• In Table 2, ◯ indicates that pattern collapse has not occurred under the corresponding condition, while x indicates that pattern collapse has occurred under the corresponding condition.
• As shown in the results of Table 2, no pattern collapse has occurred under all conditions in the experimental example 1. Meanwhile, in the comparative examples 1 and 2, pattern collapse has occurred under some specific conditions. Thus, it is clear that pattern collapse can be more effectively suppressed in the experimental example 1 than in the comparative examples 1 and 2. It is because a maximum stress σ_MAXapplied to the pattern is reduced by substituting H of an OH group on the surface of a resist pattern with a silyl group of the TMSDMA so as to improve hydrophobic property and increasing a contact angle θ of the rinse solution with respect to the pattern.
• Furthermore, in the first embodiment, since the vapor of the first processing solution is supplied, the amount of usage of the first processing solution can be reduced as compared to a case of directly supplying the first processing solution itself. By way of example, in the present embodiment, the amount of the first processing solution used for processing one sheet of wafer may be about 2.5 μl. On the contrary, if the first processing solution in a liquid phase is supplied, not a vapor, the amount of the first processing solution for processing one sheet of wafer may be about 100 μl in order to obtain the same effect. Accordingly, in accordance with the present embodiment, the amount of usage of the hydrophobicizing agent can be reduced to about 1/40, so that cost for substrate processing can be reduced greatly.
• The first embodiment has been described for the case of applying the substrate processing apparatus in accordance with the present disclosure to the developing apparatus and applying the substrate processing method in accordance with the present disclosure to the developing method. However, application of the substrate processing apparatus in accordance with the present disclosure may not be limited to the developing apparatus that performs a developing process on the substrate. By way of example, the substrate processing apparatus in accordance with the present disclosure may be also applicable to a single-substrate type cleaning apparatus that performs a cleaning process on a single substrate held on a spin chuck. When applying the substrate processing apparatus in accordance with the present disclosure to the cleaning apparatus, it may be possible to use an apparatus having the same configuration as that of the developing apparatus illustrated inFIGS. 4 and 5 excepting that it does not have the developing solution supply mechanism. Further, when applying the substrate processing method in accordance with the present disclosure to the cleaning method, the developing method described inFIG. 7 may be used while omitting the developing solution supply process.
First Modification Example of the First Embodiment
• Now, referring toFIG. 14 andFIGS. 15A to 15E, a developing apparatus and a developing method in accordance with a first modification example of the first embodiment will be explained.
• The developing apparatus in accordance with the first modification example is different from the developing apparatus in accordance with the first embodiment in that a rinse solution is removed while detecting a moving position of an interface between the rinse solution and an atmosphere when the rinse solution is scattered in the atmosphere including the vapor of the first processing solution.
• FIG. 14 is a cross sectional view illustrating a developing unit in accordance with the first modification example.FIGS. 15A to 15E are schematic diagrams illustrating a principle of a method for detecting the position of the interface between the rinse solution and the atmosphere. In the following description (including description of the other modification examples and other embodiments below), the same parts as described above will be assigned same reference numerals, and elaboration thereof will be omitted. Further, inFIG. 14, illustration of a processing chamber is omitted.
• In this modification example, units other than a developing unit DEV of a coating and developing system including the developing apparatus may be the same as those described in the first embodiment with reference toFIGS. 1 to 3.
• Meanwhile, in this first modification example, there is provided a detectingunit80 for detecting whether or not an interface B between a rinsesolution42 and an atmosphere (vapor44 of a first processing solution) is formed when a part of the rinse solution is repelled and removed and a part of the surface of a wafer W is exposed on an approximate center of the wafer W.
• Alternatively, the detectingunit80 may detect a position of the interface B between the rinsesolution42 and the atmosphere (vapor44 of the first processing solution) in order to shift a position, where thevapor44 of the first processing solution is supplied onto the wafer W, at a speed corresponding to a speed at which the rinsesolution42 is scattered and moved.
• As depicted inFIG. 14, the detectingunit80 irradiates a laser beam L to the wafer W, held on aspin chuck52, on which the rinsesolution42 has been supplied, and detects an amount of reflection light reflected from a surface of the wafer W. The detectingunit80 includes a retro-reflective laser sensor (laser generating unit)81, a reflectingplate82 and alaser receiving unit83. Thelaser generating unit81 irradiates light of the laser beam L onto the surface of the wafer W, and the reflectingplate82 reflects the laser beam L irradiated to and reflected from the surface of the wafer W. Thelaser receiving unit83 receives the reflected light of the laser beam L that is reflected by the reflectingplate82 and reflected again on the surface of the wafer W. Further, although attenuation of the laser beam may vary depending on the kind of the wafer W, the attenuation of the laser beam can be reduced by minimizing a reflection angle.
• Further, in the present modification example, the laser beam is used as the irradiation light irradiated to the wafer W. However, the irradiation light may not be limited to the laser beam, but it may be of any kind as long as it has some degree of straightforwardness. Here, instead of the retro-reflective laser sensor81 and thelaser receiving unit83, a light generating unit and a light receiving unit corresponding to the irradiation light may be used.
• The detectingunit80 is connected with a detectingboard85 via anamplifier84 so as to convert a detected analog signal into a digital signal for detection.
• The detectingboard85 includes aCPU86. TheCPU86 measures analog signals outputted from the detectingunit80 and performs an operation for comparing a value obtained when the surface of the wafer W is covered with the rinse solution immediately before the interface B is formed and a value obtained when the interface B is formed and the surface of the wafer W is thus exposed. Alternatively, theCPU86 may perform an operation for comparing any one of the analog signals with a preset threshold value. Further, the detectingboard85 is connected with acomputer88 that outputs a value of the detectingunit80 and a determination result on adisplay87 based on a signal from theCPU86.
• Further, theCPU86 controls themotor19 to rotate and move thevapor supply nozzle16, so that thevapor supply nozzle16 is rotated and moved, and theCPU86 detects a position of thevapor supply nozzle16 by detecting a rotation position of themotor19.
• Further, the detectingboard85, theCPU86, thedisplay87 and thecomputer88 and the like may be included in thecontroller30.
• Now, a developing method in accordance with the first modification example will be explained. The developing method in accordance with the present modification example is substantially the same as the developing method described in the first embodiment with reference toFIG. 7 excepting that the developing method in accordance with the first modification example is performed while the detectingunit80 detects whether or not the interface B between the rinsesolution42 and the atmosphere (vapor44 of the first processing solution) is formed. In the following, a principle of the method for detecting the position of the interface B between the rinsesolution42 and the atmosphere (vapor44 of the first processing solution) will be described with reference toFIGS. 15A to 15E.
• Before a developing solution supply process (step S11) is performed, the detectingunit80 detects a received light amount (level 0) in an OFF-state while a wafer W is held on thespin chuck52 in order to set a threshold value for noise margin that may be different depending on the kind of a wafer W (seeFIG. 15A). Thereafter, when the developing solution supply process (step S11) is performed, the detectingunit80 is operated at the moment a supply signal for a developingsolution nozzle36 is turned ON, and the detectingunit80 measures (detects) a reflection amount of a laser beam L irradiated to a surface of the wafer W immediately before the supply of a developingsolution41 from the developingsolution nozzle36 is begun (seeFIG. 15B). A measured analog signal is sent to theCPU82 and the reflection light amount is compared with the received light amount oflevel 0, and the threshold value for noise margin is set based on a difference between them. Here, the threshold value for noise margin is set by measuring (detecting) the reflection amount of the laser beam L irradiated to the surface of the wafer W immediately before the developingsolution41 is supplied from the developingsolution nozzle36. However, the timing for measuring the reflection light amount may not be limited to immediately before the supply of the developingsolution41 from the developingsolution nozzle36 is started. That is, the reflection amount of the laser beam L irradiated to the surface of the wafer W may be measured (detected) at any point in time before the developingsolution41 is supplied from the developingsolution nozzle36, and the threshold value for noise margin can be set based on the detected reflection light amount.
• Subsequently, a rinse solution supply process (step S12) and a film thickness adjusting process (step S13) are performed. A laser reflection amount is measured (detected) after a liquid film thickness of a rinsesolution42 on the surface of the wafer W is adjusted through the film thickness adjusting process (step S13). In this state, since the laser beam L is blocked by the rinsesolution42 and reflectivity decreases because of the rinsesolution42 staying on the wafer W, the reflection light amount may be almost level 0 (seeFIG. 15C).
• Thereafter, a rinse solution removing process (steps S14 to S16) is performed. While supplying thevapor44 of the first processing solution from avapor supply nozzle16, the wafer W is rotated by a drivingmotor54, so that the rinsesolution42 is scattered and removed away. In a first removing process (step S14), the wafer W is rotated while supplying thevapor44 of the first processing solution onto an approximate center of the wafer W. As a consequence, the rinsesolution42 may be scattered and removed from the approximate center of the wafer W, and the surface of the wafer W may be exposed, resulting in improvement of reflectivity. Therefore, a high level of reflection light amount is detected (seeFIG. 15D).
• In other words, if a high level of reflection light amount is detected, it may be determined that the rinsesolution42 is scattered and removed on the approximate center of the wafer W. Accordingly, when the high level of reflection light amount is detected, a second removing process (step S15) may be started. That is, the rinsesolution42 may be removed while shifting a position, where thevapor44 of the first processing solution is supplied to the wafer W, toward a periphery of the wafer W from the center of the wafer W based on the detected reflection light amount.
• Then, after a drying process (step S17) is performed and the rinsesolution42 is removed from the surface of the wafer W, the detectingunit80 is turned OFF (seeFIG. 15E).
• By using the detectingunit80 as described above, it can be detected whether the rinsesolution42 exists on the surface of the approximate center of the wafer W. Accordingly, the first removing process (step S14) can be finished and the second removing process (step S15) can be started according to the time when the interface B between the rinsesolution42 and the atmosphere (vapor44 of the first processing solution) is formed on the approximate center of the wafer W. Thus, the position where thevapor44 of the first processing solution is supplied can be moved according to the position on which the rinsesolution42 is scattered and moved. As a result, pattern collapse can be more securely suppressed when the rinsesolution42 is removed.
• Further, in this first modification example, a multiple number of the detecting units may be installed from the approximate center of the wafer W to the periphery of the wafer W so as to detect presence or absence of the rinsesolution42 at multiple positions on the wafer W. Alternatively, by rotating (moving) thelaser generating unit81 and the reflectingplate82 synchronously so as to allow angles formed between the laser beam and the surface of the wafer W to be varied synchronously, presence or absence of the rinsesolution42 may be detected at multiple positions on the wafer W. In such a case, by detecting presence or absence of the rinsesolution42 at the multiple positions on the wafer W at the respective time, a speed at which the rinsesolution42 is scattered and moved on the wafer W can be calculated. Accordingly, thevapor supply nozzle16 can be moved at a speed corresponding to a speed at which the interface B between the rinsesolution42 and the atmosphere (vapor44 of the first processing solution) is moved. Thus, by way of example, thevapor supply nozzle16 can be moved at the same speed as the speed at which the interface B between the rinsesolution42 and the atmosphere (vapor44 of the first processing solution) is moved in the third removing process (step S16). That is, the rinsesolution42 may be removed while shifting the position where thevapor44 of the first processing solution is supplied to the wafer W at the speed corresponding to the speed at which the rinsesolution42 is scattered and moved, based on the detected reflection light amount.
• In this first modification example, a surface of a resist pattern may be hydrophobicized by the vapor of the first processing solution including a hydrophobicizing agent. Accordingly, pattern collapse can be suppressed when the rinse solution is supplied onto a substrate on which fine resist patterns are formed and then the rinse solution is removed from the substrate. Furthermore, by reducing an amount of usage of the hydrophobicizing agent, cost for substrate processing can be reduced.
• Further, in accordance with the first modification example, the moving position of the interface between the rinse solution and the atmosphere can be accurately detected by the detecting unit, and the vapor supply nozzle can be moved to follow up the movement of the interface between the rinse solution and the atmosphere. Accordingly, the vapor of the first processing solution can be successfully supplied to the vicinity of the interface between the rinse solution and the atmosphere when the interface is moved. Thus, pattern collapse can be suppressed more effectively. Further, by further reducing an amount of usage of the hydrophobicizing agent, cost for substrate processing can be reduced.
• Moreover, in the present modification example, although it has been described that the present disclosure is applied to the developing apparatus, the present disclosure may not be limited to the developing apparatus but can be applied to a single-wafer cleaning apparatus that performs a cleaning process on a substrate held on a spin chuck. Furthermore, in the present modification example, although it has been described that the present disclosure is applied to the developing method, the present disclosure may not be limited to the developing method but can be applied to a single-wafer cleaning method for performing a cleaning process on a substrate held on a spin chuck.
Second Modification Example of the First Embodiment
• Now, referring toFIGS. 16 and 17, a developing apparatus and a developing method in accordance with a second modification example of the first embodiment will be described.
• The developing apparatus in accordance with the second modification example is different from the developing apparatus in accordance with the first embodiment in that a processing solution supply nozzle is provided to a vapor supply nozzle.
• FIG. 16 is a diagram schematically illustrating major parts of a developing unit in accordance with the second modification example.
• In this second modification example, units other than a developing unit DEV of a coating and developing system including the developing apparatus may be the same as those described in the first embodiment with reference toFIGS. 1 to 3. Further, the developing unit DEV in accordance with the second modification example may have the same configuration as that of the developing unit DEV of the coating and developing system in accordance with the first embodiment excepting the processing solution supply nozzle. Thus, elaboration of parts inFIG. 16 already described in the first embodiment with reference toFIGS. 4 and 5 will be omitted.
• FIG. 16 schematically illustrates nozzle positions when a rinse solution removing process is performed after a developing solution supply process to a film thickness adjusting process are performed as will be described below with reference toFIG. 17. That is, a developingsolution nozzle36 is located outside a cup CP; a rinsenozzle15 is located at a position slightly deviated toward a periphery of a wafer W from an approximate center of a wafer W; and avapor supply nozzle16 is placed at position above the approximate center of the wafer W.
• In the second modification example, aprocessing solution nozzle16ais provided next to thevapor supply nozzle16. Theprocessing solution nozzle16a, held by a non-illustrated nozzle holder, is fixed at a leading end of a non-illustrated nozzle scan arm. Theprocessing solution nozzle16asupplies a second processing solution42ahaving a smaller surface tension than that of the rinsesolution42 on a surface of the wafer W. As in the case of thevapor supply nozzle16, this nozzle scan arm may be rotatable about a non-illustrated motor in a θ direction by the motor. The second processing solution42ais supplied into theprocessing solution nozzle16afrom a non-illustrated second processing solution supply mechanism through a non-illustrated supply pipe. Alternatively, theprocessing solution nozzle16amay be fixed at a leading end of thenozzle scan arm18 together with thevapor supply nozzle16.
• By way of example, the aforementioned HFE-based solvent having a smaller surface tension than that of the rinsesolution42 such as pure water may be used as the second processing solution42a. Further, xylene, hexamethyldisilazane (HMDS) or the like may also be used.
• Moreover, theprocessing solution nozzle16aserves as a second processing solution supply unit in the present disclosure.
• Now, a developing method in accordance with the second modification example will be discussed with reference toFIG. 17.FIG. 17 is a flowchart for describing a process sequence.
• As depicted inFIG. 17, the developing method in accordance with the second modification example may include a developing solution supply process (step S21), a rinse solution supply process (step S22), a second processing solution supply process (step S23), a film thickness adjusting process (step S24), a rinse solution removing process (steps S25 to S27) and a drying process (step S28). The rinse solution removing process may include a first removing process (step S25), a second removing process (step S26) and a third removing process (step S27).
• First, the developing solution supply process (step S21) and the rinse solution supply process (step S22) are performed. The developing solution supply process (step S21) and the rinse solution supply process (step S22) may be carried out in the same ways as steps S11 and S12 in the first embodiment, respectively.
• Then, the second processing solution supply process (step S23) is performed. In the second processing solution supply process (step S23), the second processing solution42ais supplied onto the wafer W on which the rinsesolution42 has been already supplied.
• The developingsolution nozzle36 is moved out of the cup CP, and theprocessing solution nozzle16ais moved to a position above the approximate center of the wafer W. Then, the second processing solution42ais supplied while the wafer W is being rotated. Since the supply of the second processing solution42ais carried out while rotating the wafer W, the surface of the wafer W may be rinsed by the rinsesolution42 including the second processing solution42a.
• By way of example, a liquid film of the rinsesolution42 including the second processing solution42ais formed on the surface of the wafer W, and a rotation speed of the wafer W may be set to be relatively low, e.g., about 0 rpm to about 1200 rpm, and more desirably, about 500 rpm so as not to allow a top surface of a developed resist pattern to be exposed out of the rinsesolution42. By rotating the wafer W at the relatively low speed of about 0 rpm to about 1200 rpm, a flow velocity of the rinsesolution42 including the second processing solution42aon the wafer W can be reduced, thus preventing collapse of a resistpattern29 when the rinsesolution42 including the second processing solution42ais flown.
• Further, in the second processing solution supply process (step S23), a large amount of second processing solution42amay be supplied so as to substantially substitute the rinsesolution42 with the second processing solution42a. On the contrary, in the second processing solution supply process (step S23), the second processing solution42amay be just dripped on the wafer W on which the rinsesolution42 has been supplied. When dripping thesecond processing solution42 on the wafer W, the second processing solution supply process (step S23) may not be performed prior to the rinse solution removing process, but it may be performed concurrently with the rinse solution removing process. That is, the rinse solution removing process (steps25 to27) may be performed while dripping the second processing solution42afrom theprocessing solution nozzle16awithout performing step S23.
• Subsequently, the film thickness adjusting process (step S24) is carried out. The film thickness adjusting process (step S24) may be substantially the same as the film thickness adjusting process (step S13) in accordance with the first embodiment. In this film thickness adjusting process (step S24), the supply of the second processing solution42ais stopped, and a part of the rinsesolution42 including the second processing solution42ais scattered away by rotating the wafer W, and, thus, a thickness of the liquid film of the rinsesolution42 is adjusted.
• Thereafter, the rinse solution removing process (steps25 to27) is performed. In the rinse solution removing process (steps25 to27), the wafer W is rotated whilevapor44 of a first processing solution is supplied onto the wafer W, so that the rinsesolution42 including the second processing solution42ais scattered (spun) and removed away, as in the rinse solution removing process (steps S14 to S16) in accordance with the first embodiment.
• Then, the drying process (step S28) is performed. In the drying process (step S28), the wafer W is dried by being rotated at a preset rotational speed, as in the drying process (step S17) in the first embodiment.
• In the second modification example, the surface of the resist pattern may be hydrophobicized by the vapor of the first processing solution including a hydrophobicizing agent. Accordingly, pattern collapse can be suppressed when the rinse solution is supplied onto a substrate on which fine resist patterns are formed and then the rinse solution is removed from the substrate. Furthermore, by reducing an amount of usage of the hydrophobicizing agent, cost for substrate processing can be reduced.
• In this second modification example, the second processing solution having a smaller surface tension than that of the rinse solution is supplied, and in the rinse solution removing process, the rinse solution including the second processing solution is scattered and removed by rotating the wafer W while supplying the vapor of the first processing solution including the hydrophobicizing agent. The rinse solution including the second processing solution has a smaller surface tension than that of the rinse solution. Accordingly, when the rinse solution is supplied onto the substrate on which fine resist patterns are formed and when the rinse solution is removed from this substrate, pattern collapse can be suppressed more securely.
• Furthermore, HFE has a larger specific gravity than that of pure water. Accordingly, when HFE is used as the second processing solution, the second processing solution may be positioned under the rinse solution after the second processing solution supply process (step S23), thereby allowing the rinse solution to easily escape from the resist pattern. Thus, the effect of preventing pattern collapse can be further improved.
• Moreover, in the present modification example, although it has been described that the present disclosure is applied to the developing apparatus, the present disclosure may not be limited to the developing apparatus but can be applied to a single-wafer cleaning apparatus that performs a cleaning process on a substrate held on a spin chuck. Furthermore, in the present modification example, although it has been described that the present disclosure is applied to the developing method, the present disclosure may not be limited to the developing method but can be applied to a single-wafer cleaning method for performing a cleaning process on a substrate held on a spin chuck.
Second Embodiment
• Now, a developing apparatus and a developing method in accordance with a second embodiment of the present disclosure will be described with reference toFIGS. 18 to 22B.
• The developing apparatus in accordance with the second embodiment is different from the developing apparatus in accordance with the first embodiment in that a rinse solution is scattered while a position where vapor of a first processing solution is supplied by a vapor supply nozzle is being shifted from a periphery of a wafer toward a center of the wafer.
• FIG. 18 is a diagram schematically illustrating major parts of a developing unit in accordance with the second embodiment.FIG. 19 is a perspective view illustrating an example vapor supply nozzle provided with a strip-shaped discharge opening.
• In this second embodiment, units other than a developing unit DEV of a coating and developing system may be substantially the same as those described in the first embodiment with reference toFIGS. 1 to 3. Further, the developing unit DEV in accordance with the second embodiment may have the same configuration as that of the developing unit DEV of the coating and developing system in accordance with the first embodiment. Thus, elaboration of parts inFIG. 18 already described in the first embodiment with reference toFIGS. 4 and 5 will be omitted.
• FIG. 18 schematically illustrates nozzle positions when a rinse solution removing process is performed after a developing solution supply process and a rinse solution supply process are performed as will be described below with reference toFIG. 20. That is, a developingsolution nozzle36 is located outside a cup CP; a rinsenozzle15 is located at a position above an approximate center of a wafer W; and avapor supply nozzle16bis located at a position above an approximate edge of the wafer W.
• Thevapor supply nozzle16bis moved above the wafer W from the periphery of the wafer W toward the center of the wafer W in a spiral shape. Thevapor supply nozzle16bmay have a strip-shaped discharge opening in a diametric direction of the wafer W. Below, an example vapor supply nozzle provided with a strip-shaped discharge opening will be explained with reference toFIG. 19.
• As depicted inFIG. 19, thevapor supply nozzle16bis formed in, e.g., a wedge shape such that its width decreases toward a bottom thereof, and a strip-shaped (slit-shaped)discharge opening16cfor supplyingvapor44 of the first processing solution is provided in a bottom surface of thevapor supply nozzle16b. Thedischarge opening16cis arranged such that its lengthwise direction is oriented toward the center of the wafer W from the periphery thereof.
• Further, a temperature control may be performed by using adouble pipe16fincluding aninner pipe16dand anouter pipe16eso as to set a temperature of thevapor44 of the first processing solution to be a preset value depending on the kind of the wafer W, a resist pattern and/or the rinse solution. Temperature-controlled hot water supplied from a non-illustrated hot water supply source flows through the outer pipe6e, and thevapor44 of the first processing solution supplied from avapor supply mechanism33 flows through theinner pipe16d. Further, the temperature-controlled hot water is returned back into the hot water supply source through areturn pipe16g. Thevapor supply nozzle16dhaving the above-described configuration may be used in other embodiments or modification examples.
• Now, a developing method in accordance with the second embodiment will be described with reference toFIGS. 20 to 22B.FIG. 20 provides a flowchart to describe a process sequence.FIGS. 21A to 21D are side views andFIGS. 22A and 22B are plane views for illustrating respective processes.
• As depicted inFIG. 20, the developing method in accordance with the second embodiment may include a developing solution supply process (step S31), a rinse solution supply process (step S32), a rinse solution removing process (steps S33 to S35) and a drying process (step S36). The rinse solution removing process may include a first removing process (step S33), a second removing process (step S34) and a third removing process (step S35).
• First, the developing solution supply process (S31) and the rinse solution supply process (S32) are performed. The developing solution supply process (S31) and the rinse solution supply process (S32) may be carried out in the same ways as steps S11 and S12 in accordance with the first embodiment, respectively.
• Then, the rinse solution removing process (steps S33 to S35) is performed. In this rinse solution removing process (steps S33 to S35), in the state that the rinsesolution42 is being supplied onto an approximate center of a wafer W, a rinsesolution42 is scattered while shifting a position, where thevapor44 of the first processing solution is supplied to the wafer W, from a periphery of the wafer W toward the approximate center of the wafer W.
• The first removing process (step S33) is performed first. In the first removing process (step S33), in the state that the rinsesolution42 is being supplied onto the approximate center of the wafer W, the wafer W is rotated while supplying thevapor44 of the first processing solution onto an approximate edge of the wafer W, so that the rinsesolution42 is scattered away.
• As illustrated inFIG. 21A, in the state that a rinsenozzle15 above the approximate center of the wafer W is supplying the rinsesolution42 onto the wafer W, the wafer W is rotated by a drivingmotor54 at a rotation speed of, e.g., about 0 rpm to about 200 rpm, desirably, about 100 rpm while thevapor supply nozzle16bmoved to an approximate edge of the wafer W is supplying thevapor44 of the first processing solution to the edge of the wafer W.
• As illustrated inFIG. 21A, if thevapor44 of thefirst processing solution44 is supplied and a concentration, i.e., a pressure of thevapor44 of thefirst processing solution44 increases at the approximate edge of the wafer W, the rinsesolution42 may be moved to a center of the wafer W in which the concentration, i.e., the pressure of thevapor44 of the first processing solution is low. As a result, a liquid film of the rinse solution may be recessed at the approximate edge of the wafer W, so that a thickness of the liquid film at the approximate edge of the wafer W would be reduced, whereas the thickness of the liquid film at the center portion of the wafer W would be increased. Then, if thevapor44 of the first processing solution continues to be supplied, a part of the rinsesolution42 may be repelled on the approximate edge of the wafer W and a part of the surface of the wafer W may be exposed, so that an interface B between the rinsesolution42 and an atmosphere (vapor44 of the first processing solution) may be formed on the surface of the wafer W, as illustrated inFIG. 21B. Further, the rinsesolution42 may be rotatably scattered from the exposed surface of the wafer W at the approximate edge thereof.
• Further, in the present embodiment, if the concentration of thevapor44 of the first processing solution increases on the wafer W, thevapor44 of the first processing solution may be mixed with the rinsesolution42, resulting in reduction of a surface tension of the rinsesolution42. Moreover, if the concentration of thevapor44 of the first processing solution increases on the wafer W, thevapor44 of the first processing solution may be mixed with the rinsesolution42 and the mixture may reach the surface of the resistpattern29 on the wafer W and may hydrophobicize the surface of the resistpattern29.
• InFIGS. 21A to 21D, thevapor44 of the first processing solution supplied from thevapor supply nozzle16bis shown to have a certain area for the purpose of illustration. Since, however, thevapor44 of the first processing solution diffuses as a gas, there exists no clear boundary.
• Subsequently, the second removing process (step S34) is performed. In the second removing process (step S34), in the state that the rinsesolution42 is being supplied onto the approximate center of the wafer W, the wafer W is rotated, while shifting a position, where thevapor44 of the first processing solution is supplied to the wafer W, from the periphery of the wafer W toward the center of the wafer W. As a result, the rinsesolution42 is scattered away.
• As illustrated inFIG. 21C, in the state that the rinsenozzle15 above the approximate center of the wafer W is supplying the rinsesolution42 onto the wafer W and thevapor supply nozzle16bis supplying thevapor44 of the first processing solution onto the wafer W, the wafer W is rotated by the drivingmotor54 at a rotation speed of, e.g., about 0 rpm to about 200 rpm, more desirably, about 100 rpm while thevapor supply nozzle16bis moved toward the approximate center of the wafer W.
• Further, in the second removing process (step34), the rinsesolution42 may be rotatably scattered from the exposed surface of the wafer W at the approximate edge thereof as illustrated inFIG. 22A, as in the first removing process (step S33). The interface B between the rinsesolution42 and the atmosphere (vapor44 of the first processing solution) is moved on the surface of the wafer W from the periphery of the wafer W toward the center of the wafer W to follow up the movement of thevapor supply nozzle16b.
• Then, the third removing process (step S55) is performed. In the third removing process (step S35), when the position where thevapor44 of the first processing solution is supplied to the wafer W reaches the approximate center of the wafer W, the rinsesolution42 is scattered away by rotating the wafer W while slightly moving therise nozzle15 from the approximate center of the wafer W toward a periphery of the wafer W.
• In other words, in the state that thevapor supply nozzle16bis supplying thevapor44 of the first processing solution, the rinsenozzle15 is slightly moved from the approximate center of the wafer W toward the periphery of the wafer W when thevapor supply nozzle16breaches the approximate center of the wafer W, as illustrated inFIG. 21D. As a result, hydrophobicization of the surface of the resistpattern29 may be completed on the entire surface of the wafer W, and the rinsesolution42 to be scattered as a result of the rotation of the wafer W may not be accumulated on the wafer W, but may be scattered off the wafer W while being rotated on the surface of the wafer W, as depicted inFIG. 22B.
• Thereafter, the drying process (step S36) is performed. In the drying process (step S36), a drying process is performed by rotating the wafer W at a preset rotation speed, as in the drying process (step S17) in accordance with the first embodiment.
• After the third removing process (step S35) is performed, the surface of the resistpattern29 is hydrophobicized on the entire surface of the wafer W. Accordingly, a rinse solution supply process may be additionally performed between the third removing process (step S35) and the drying process (step S36). Even if the rinse solution is removed after the additional rinse solution supply process, pattern collapse can be prevented.
• In the second embodiment, a moving speed of thevapor supply nozzle16bthat is moved from the edge of the wafer W toward the center of the wafer W is set so as to allow thedischarge opening16cto reach the approximate center of the wafer W in about 1 to about 5 seconds in case of the 12 inch wafer W, for example). Accordingly, by way of example, a rotation speed of the wafer W and the moving speed of the nozzle may be determined by, e.g., calculation or by previous experiment based on a length of the strip-shaped discharge opening16cso as to allow thevapor44 of the first processing solution to be discharged on the entire surface of the wafer W without missing parts in a radial direction thereof. At this time, thevapor44 of the first processing solution discharged from thedischarge opening16cin a strip shape may be diffused on the entire surface of the wafer W without missing parts from an outer side toward an inner side thereof. As a result, a hydrophobicized part of the surface of the resistpattern29 by thevapor44 of the first processing solution may be expanded from the edge of the wafer W toward the center of the wafer W in a spiral shape on the entire surface of the wafer W.
• In this second embodiment, the surface of the resist pattern may be hydrophobicized by the vapor of the first processing solution including a hydrophobicizing agent. Accordingly, pattern collapse can be suppressed when the rinse solution is supplied onto a substrate on which fine resist patterns are formed and then the rinse solution is removed from the substrate. Furthermore, by reducing an amount of usage of the hydrophobicizing agent, cost for substrate processing can be reduced.
• Further, in the second embodiment, in the state that the rinse solution is being supplied onto the approximate center of the wafer W, the rinse solution is scattered and removed while shifting the position, where the vapor of the first processing solution is supplied to the wafer W, from the periphery of the wafer toward the center of the wafer. The interface between the rinse solution and the atmosphere is also automatically moved on the wafer W from the periphery of the wafer W toward the center of the wafer W to follow up the movement of the vapor supply nozzle, so that the interface between the rinse solution and the atmosphere may not be moved to the center of the wafer W ahead of the vapor supply nozzle. Accordingly, when the rinse solution is supplied onto the substrate on which fine resist patterns are formed and when the rinse solution is removed from this substrate, pattern collapse can be suppressed more securely.
• Moreover, in the present embodiment, although it has been described that the present disclosure is applied to the developing apparatus, the present disclosure may not be limited to the developing apparatus but can be applied to a single-wafer cleaning apparatus that performs a cleaning process on a substrate held on a spin chuck. Furthermore, in the present embodiment, although it has been described that the present disclosure is applied to the developing method, the present disclosure may not be limited to the developing method but can be applied to a single-wafer cleaning method for performing a cleaning process on a substrate held on a spin chuck.
Third Embodiment
• Now, referring toFIGS. 23 to 25, a developing apparatus and a developing method in accordance with a third embodiment will be described.
• The developing apparatus in accordance with the third embodiment is different from the developing apparatus in accordance with the first embodiment in that it includes a nozzle unit having a vapor supply nozzle of an elongated shape and a suction nozzle at a front side in a moving direction of the nozzle unit.
• FIG. 23 is a diagram schematically illustrating major parts of a developing apparatus in accordance with the third embodiment.FIGS. 24A and 24B are enlarged views of the nozzle unit.
• In the third embodiment, units other than a developing unit DEV of a coating and developing system including the developing apparatus may be the same as those described in the first embodiment with reference toFIGS. 1 to 3. Further, except the vicinities of the vapor supply nozzle, the developing unit DEV in accordance with the third embodiment may have the same configuration as that of the developing unit DEV of the coating and developing system in accordance with the first embodiment. Thus, elaboration of parts inFIG. 23 already described in the first embodiment with reference toFIGS. 4 and 5 will be omitted.
• FIG. 23 schematically illustrates nozzle positions when a rinse solution removing process is performed after a developing solution supply process and a rinse solution removing process are performed as will be described below with reference toFIG. 25. That is, a developingsolution nozzle36 is located outside a cup CP; a rinsenozzle15 is located at a position above an approximate center of a wafer W; and anozzle unit160 including a vapor supply nozzle is located at a position above an approximate edge of the wafer W.
• As depicted inFIGS. 23 and 24A, thenozzle unit160 includes afirst discharge nozzle161, afirst suction nozzle162, asecond discharge nozzle163, asecond suction nozzle164 and athird discharge nozzle165. Thenozzle unit160 including the respective nozzles is configured to be movable above the wafer W in a direction C (hereinafter, referred to as a “moving direction”). Further, each of the nozzles may have an elongated shape having a length substantially the same as a diameter of the wafer W. The nozzles are arranged in a direction that intersects an elongated direction of the elongated nozzles. Furthermore, the nozzles may be configured to be movable all together in the direction (arrangement direction of each nozzle and direction substantially parallel with the diametric direction of the wafer W) that intersects the elongated direction of the nozzles. Alternatively, as long as a preceding and following relationship to be described below is satisfied, some of the nozzles may be move together, while the others are moved separately from them. Still alternatively, the nozzles may be configured to be movable all individually.
• Thefirst discharge nozzle161supplies vapor44 of a first processing solution onto a wafer W. Thefirst discharge nozzle161 serves as a vapor supply unit in accordance with the present disclosure.
• Thefirst suction nozzle162 is configured to be movable on the front side of thefirst discharge nozzle161 in the moving direction C of thenozzle unit160. Thefirst suction nozzle162 sucks in a rinsesolution42, and serves as a suction unit and a rinse solution removing unit in accordance with the present disclosure.
• Thesecond discharge nozzle163 is configured to be movable on the rear side of thefirst discharge nozzle161 in the moving direction C of thenozzle unit160. Thesecond discharge nozzle163 supplies a second rinsesolution42bonto the wafer W from which the rinsesolution42 has been removed. Thesecond suction nozzle164 is configured to be movable on the rear side of thefirst discharge nozzle161 in the moving direction C of thenozzle unit160, and thesecond suction nozzle164 sucks and removes the second rinsesolution42bsupplied on the wafer W. In this third embodiment, thesecond suction nozzle164 is divided into twonozzles164aand164b, and these twosecond suction nozzles164aand164bare respectively provided on the front side and on the rear side of thesecond discharge nozzle163 in the moving direction C of thenozzle unit160.
• Thethird discharge nozzle165 is configured to be movable on the rear side of thesecond discharge nozzle163 and thesecond suction nozzle164 in the moving direction C of thenozzle unit160. Thethird discharge nozzle165 supplies a gas G onto the wafer W from which the second rinsesolution42bhas been removed and thus dries the wafer W.
• In order to prevent pattern collapse and reduce an amount of usage of thefirst processing solution43, the nozzle unit may have only thefirst discharge nozzle161 and thefirst suction nozzle162. That is, the nozzle unit may not include the second discharge nozzle, the second suction nozzle and the third discharge nozzle.FIG. 24B illustrates anexample nozzle unit160ahaving only afirst discharge nozzle161 and afirst suction nozzle162 without having a second discharge nozzle, a second suction nozzle and a third discharge nozzle.
• Further, in this embodiment, a rinsenozzle15 is provided separately from thenozzle unit160. However, the rinse nozzle may be provided on a front side of all nozzles included in the nozzle unit in a direction in which the nozzle unit is moved above a wafer W. Accordingly, the rinse nozzle may be included in the nozzle unit. In such a case, the rinse nozzle may have an elongated shape having a length substantially the same as a diameter of the wafer W like the first discharge nozzle. A driving motor for rotating aspin chuck52 may be omitted, as illustrated inFIG. 23.
• Now, a developing method in accordance with the third embodiment will be explained with reference toFIGS. 24A and 25.FIG. 25 provides a flowchart to describe a process sequence.
• As described inFIG. 25, the developing method in accordance with the third embodiment may include a developing solution supply process (step S41), a rinse solution supply process (step S42), a rinse solution removing process (step S43), a second rinse solution removing process (step S44) and a drying process (step S45).
• In the aforementioned processes, the rinse solution removing process (step S43) to the drying process (step S45) are mentioned in sequence at positions on the wafer W. In accordance with the present embodiment, however, while thenozzle unit160 is being moved above the wafer W from one side to the other, the processes are performed. The rinse solution removing process (step S43) to the drying process (step S45) may be performed at different positions on the wafer W simultaneously. Accordingly, the following description will be provided at the positions where the wafer W is located.
• First, the developing solution supply process (step S41) and the rinse solution supply process (S42) are performed. The developing solution supply process (step S41) and the rinse solution supply process (step S42) may be performed in the same ways as the developing solution supply process (step S11) and the rinse solution supply process (step S12) in accordance with the first embodiment.
• Then, the rinse solution removing process (step S43) is performed. In the rinse solution removing process (step S43), while supplying thevapor44 of the first processing solution from the firstelongated discharge nozzle161 that is being moved, the rinsesolution42 is removed by sucking the rinsesolution42 by the firstelongated suction nozzle162 that is being moved on the front side of thefirst discharge nozzle161. The rinse solution removing process (step S43) to the drying process (step S45) are performed without rotating the wafer W.
• Further, the third embodiment is described for the case of sucking and removing the rinse solution while supplying the vapor of the first processing solution onto the wafer W. However, the rinse solution may be sucked in after the vapor of the first processing solution is supplied. In such a case, although the rinse solution may not be sucked in while the vapor of the first processing solution is being supplied, the rinse solution may be sucked in and removed under an atmosphere including the vapor of the first processing solution.
• Subsequently, the second rinse solution removing process (step S44) is performed. In the second rinse solution removing process (step S44), while supplying the second rinsesolution42bsuch as pure water by the secondelongated discharge nozzle163 that is being moved on the rear side of thefirst discharge nozzle161, the second rinsesolution42bis removed by sucking in the second rinsesolution42bby the secondelongated suction nozzles164aand164bthat is being moved on the rear side of the first discharge nozzle151.
• Thereafter, the drying process (step S45) is performed. In the drying process (step S45), a gas such as N₂is supplied by the thirdelongated discharge nozzle164 that is being moved on the rear side of thesecond discharge nozzle163 and thesecond suction nozzle164 to dry the wafer W.
• In this third embodiment, the surface of the resist pattern may be hydrophobicized by the vapor of the first processing solution including a hydrophobicizing agent. Accordingly, pattern collapse can be suppressed when the rinse solution is supplied onto a substrate on which fine resist patterns are formed and then the rinse solution is removed from the substrate. Furthermore, by reducing an amount of usage of the hydrophobicizing agent, cost for substrate processing can be reduced.
• Furthermore, in the third embodiment as described above, the rinse solution is removed by sucking in the rinse solution by the suction nozzle. Accordingly, even in the cases that a processing target object is not of a circular shape or a center of gravity of the processing target object is not located at the center thereof, a process can be performed without rotating a processing target object, and pattern collapse can be still prevented. Furthermore, by reducing an amount of usage of the hydrophobicizing agent, cost for substrate processing can be reduced.
• Moreover, in the present embodiment, although it has been described that the present disclosure is applied to the developing apparatus, the present disclosure may not be limited to the developing apparatus but can be applied to a single-wafer cleaning apparatus that performs a cleaning process on a substrate held on a spin chuck. Furthermore, in the present embodiment, although it has been described that the present disclosure is applied to the developing method, the present disclosure may not be limited to the developing method but can be applied to a single-wafer cleaning method for performing a cleaning process on a substrate held on a spin chuck.
Fourth Embodiment
• Now, a developing apparatus and a developing method in accordance with a fourth embodiment will be described with reference toFIGS. 26 to 28.
• The developing apparatus in accordance with the fourth embodiment is different from the developing apparatus in accordance with the first embodiment in that a rinse solution is removed by rotating a substrate approximately in a half-turn and a nozzle unit including a discharge nozzle and a suction nozzle having elongated shapes is positioned to cross an approximate center of the substrate.
• FIG. 26 is a diagram schematically illustrating major parts of a developing unit in accordance with the fourth embodiment.FIG. 27 is a plane view schematically illustrating a vapor supply nozzle.
• FIG. 26 schematically illustrates nozzle positions when a rinse solution removing process is performed after a developing solution supply process and a rinse solution supply process are performed as will be described below with reference toFIG. 28. That is, a developingsolution nozzle36 is located outside a cup CP; a rinsenozzle15 is located at a position above an approximate edge of a wafer W; and anozzle unit170 including adischarge nozzle171 is placed at a position above an approximate center of the wafer W.
• As depicted inFIGS. 26 and 27, thenozzle unit170 includes thedischarge nozzle171 and twosuction nozzles172. Thedischarge nozzle171 is an elongated nozzle installed to cross an approximate center of the wafer W and provided with anelongated discharge opening173 having a length substantially the same as a diameter of the wafer W. Thedischarge nozzle171 serves as a vapor supply unit in accordance with the present disclosure.
• As depicted inFIGS. 26 and 27, the twosuction nozzles172 are respectively installed on a front side and on a rear side of thedischarge nozzle171 in a direction that intersects an elongated direction of thedischarge nozzle171. Eachsuction nozzle172 has an elongated shape and has a length substantially the same as that of thedischarge nozzle171. Further, eachsuction nozzle172 is provided with anelongated suction opening174 and sucks in and removes a rinsesolution42 supplied on the wafer W. The suction nozzles172 serve as a suction unit and a rinse solution removing unit in accordance with the present disclosure.
• Asupply opening175 for supplyingvapor44 of a first processing solution into thedischarge nozzle171 is provided above the discharge opening173 of thedischarge nozzle171. Thevapor44 of the first processing solution supplied into the discharge opening173 from avapor supply mechanism33 via thesupply opening175 is diffused to both sides of thedischarge opening173 in an elongated direction of thedischarge opening173. As depicted inFIG. 27, thesupply opening175 may not be provided at an approximate center of the wafer W but may be provided at a position slightly deviated from the approximate center of the wafer W toward a periphery of the wafer W in the elongated direction of thedischarge opening173. With this configuration, a surface of a resistpattern29 can be uniformly hydrophobicized on the entire surface of the wafer W when the rinsesolution42 is removed by rotating the wafer W approximately in a half-turn.
• An outlet opening176 for draining the rinsesolution42 from thesuction nozzle172 is provided at a position above thesuction opening174 of thesuction nozzle172. The rinsesolution42 sucked into thesuction opening174 may be collected in one place in the elongated direction of thesuction opening174 and may be drained through theoutlet opening176 by adrain unit177. As depicted inFIG. 27, theoutlet opening176 may be provided at one end of thesuction opening174 in the elongated direction of thesuction opening174. To elaborate, as shown inFIG. 27, theoutlet opening176 may be provided at a position where the rinsesolution42 is sucked at the last when the wafer W is rotated substantially in a half-turn. With this configuration, the rinsesolution42 can be completely removed from the entire surface of the wafer W when the wafer W is rotated approximately in a half-turn.
• Now, a developing method in accordance with the fourth embodiment will be described with reference toFIGS. 27 and 28.FIG. 28 provides a flowchart to describe a process sequence.
• As depicted inFIG. 28, the developing method in accordance with the fourth embodiment may include a developing solution supply process (step S51), a rinse solution supply process (step S52), a film thickness adjusting process (step S53) and a rinse solution removing process (step S54).
• First, the developing solution supply process (step S51) to the film thickness adjusting process (step S53) are performed. The developing solution supply process (step S51) to the film thickness adjusting process (step S53) may be performed in the same ways as the developing solution supply process (step S11) to the film thickness adjusting process (step S13) in accordance with the first embodiment.
• Then, the rinse solution removing process (step S54) is performed. In the rinse solution removing process (step S54), while supplying thevapor44 of the first processing solution by theelongated discharge nozzle171 installed to cross the approximate center of the wafer W when the wafer W is rotated approximately in a half-turn, the rinsesolution42 supplied on the wafer W is removed by sucking the rinsesolution42 by the twoelongated suction nozzles172 installed on the front side and on the rear side of thedischarge nozzle171 in the direction that intersects the elongated direction of thedischarge nozzle171.
• As illustrated inFIG. 27, while supplying thevapor44 of the first processing solution onto the wafer W by thedischarge nozzle171 and sucking in the rinsesolution42 from the wafer W by thesuction nozzles172, the wafer W is rotated by a drivingmotor54 approximately in a half-turn at a low speed of, e.g., about 30 rpm. Accordingly, at positions where the wafer W is located, the rinsesolution42 can be removed by sucking the rinsesolution42 by thesuction nozzles172 immediately after thevapor44 of the first processing solution is supplied by thedischarge nozzle171.
• Further, the fourth embodiment has been described for the case of removing the rinse solution by rotating the wafer approximately in a half-turn. However, in case that four discharge nozzles having elongated shapes may be arranged crosswise and a suction nozzle is installed to surround the discharge nozzles, the rinse solution may be removed by rotating the wafer W approximately in a quarter-turn. Thus, by designing shapes of the discharge nozzle and the suction nozzle appropriately, the rinse solution can be removed by rotating the wafer by a certain angle.
• In the fourth embodiment, the surface of the resist pattern may be hydrophobicized by the vapor of the first processing solution including a hydrophobicizing agent. Accordingly, pattern collapse can be suppressed when the rinse solution is supplied onto a substrate on which fine resist patterns are formed and then the rinse solution is removed from the substrate. Furthermore, by reducing an amount of usage of the hydrophobicizing agent, cost for substrate processing can be reduced.
• Furthermore, in the fourth embodiment as described above, the rinse solution is removed by sucking the rinse solution by the suction nozzle. Accordingly, when it is necessary to perform a process without rotating a processing target object, pattern collapse can be still prevented. Furthermore, by reducing an amount of usage of the hydrophobicizing agent, cost for substrate processing can be reduced.
• Moreover, in the present embodiment, although it has been described that the present disclosure is applied to the developing apparatus, the present disclosure may not be limited to the developing apparatus but can be applied to a single-wafer cleaning apparatus that performs a cleaning process on a substrate held on a spin chuck. Furthermore, in the present embodiment, although it has been described that the present disclosure is applied to the developing method, the present disclosure may not be limited to the developing method but can be applied to a single-wafer cleaning method for performing a cleaning process on a substrate held on a spin chuck.
• While various aspects and embodiments have been described herein, other aspects and embodiments will be apparent to those skilled in the art. The various aspects and embodiments disclosed herein are for the purposes of illustration and are not intended to be limiting. Therefore, the true scope of the disclosure is indicated by the appended claims rather than by the foregoing description, and it shall be understood that all modifications and embodiments conceived from the meaning and scope of the claims and their equivalents are included in the scope of the disclosure.

Claims (13)

What is claimed is:

1. A substrate processing apparatus comprising:

a substrate holder configured to hold a substrate on which a resist pattern is formed;

a rinse solution supply unit configured to supply a rinse solution onto the substrate held by the substrate holder;

a vapor supply unit configured to supply vapor of a first processing solution, which hydrophobicizes the resist pattern, onto the substrate on which the rinse solution is supplied from the rinse solution supply unit; and

a rinse solution removing unit configured to remove the rinse solution from the substrate in an atmosphere including the vapor of the first processing solution supplied from the vapor supply unit.

2. The substrate processing apparatus ofclaim 1, wherein the rinse solution removing unit removes the rinse solution while the vapor of the first processing solution is being supplied onto the substrate by the vapor supply unit.

3. The substrate processing apparatus ofclaim 1, wherein the rinse solution removing unit is a rotating unit that scatters and removes the rinse solution by rotating the substrate holder holding the substrate.

4. The substrate processing apparatus ofclaim 3, wherein the rotating unit removes the rinse solution while the vapor of the first processing solution is supplied onto a center portion of the substrate by the vapor supply unit.

5. The substrate processing apparatus ofclaim 4, further comprising:

a moving unit configured to move the vapor supply unit above the substrate,

wherein the rotating unit removes the rinse solution while a position, where the vapor of the first processing solution is supplied from the vapor supply unit, is being shifted from the center portion of the substrate toward a peripheral portion of the substrate by the moving unit.

6. The substrate processing apparatus ofclaim 5, wherein the rotating unit removes the rinse solution while the position, where the vapor of the first processing solution is supplied from the vapor supply unit, is being shifted at a speed corresponding to a speed at which the rinse solution is scattered and moved.

7. The substrate processing apparatus ofclaim 5, further comprising:

a detecting unit configured to detect an amount of light irradiated to and reflected from a surface of the substrate,

wherein the rotating unit removes the rinse solution while the position, where the vapor of the first processing solution is supplied, is being shifted based on the amount of light detected by the detecting unit.

8. The substrate processing apparatus ofclaim 3, further comprising:

a second processing solution removing unit configured to supply a second processing solution, which has a smaller surface tension than that of the rinse solution, onto the substrate on which the rinse solution is supplied from the rinse solution supply unit,

wherein the rotating unit removes the second processing solution.

9. The substrate processing apparatus ofclaim 3, further comprising:

a moving unit configured to move the vapor supply unit above the substrate,

wherein in a state that the rinse solution is being supplied onto a center portion of the substrate by the rinse solution supply unit, the rotating unit removes the rinse solution while the position, where the vapor of the first processing solution is supplied from the vapor supply unit, is being shifted from a peripheral portion of the substrate toward the center portion of the substrate by the moving unit.

10. The substrate processing apparatus ofclaim 1, wherein the rinse solution removing unit is a suction unit that removes the rinse solution by sucking the rinse solution from the substrate.

11. The substrate processing apparatus ofclaim 10, wherein the vapor supply unit is a first discharge nozzle that has an elongated shape and is configured to be movable above the substrate in one direction, and

the suction unit is a first suction nozzle of an elongated shape that is configured to be movable at a front side of the first discharge nozzle in the one direction and that removes the rinse solution by sucking the rinse solution while the vapor of the first processing solution is being supplied by the first discharge nozzle.

12. The substrate processing apparatus ofclaim 11, further comprising:

a second discharge nozzle of an elongated shape that is configured to be movable at a rear side of the first discharge nozzle in the one direction and supplies a second rinse solution onto the substrate from which the rinse solution is removed;

a second suction nozzle of an elongated shape that is configured to be movable at the rear side of the first discharge nozzle in the one direction and removes the second rinse solution by sucking the second rinse solution supplied on the substrate from the second discharge nozzle; and

a third discharge nozzle of an elongated shape that is configured to be movable at a rear side of the second discharge nozzle and a rear side of the second suction nozzle in the one direction and dries the substrate by supplying a gas onto the substrate from which the second rinse solution is removed.

13. The substrate processing apparatus ofclaim 10, further comprising:

a rotating unit configured to rotate the substrate holder holding the substrate,

wherein the vapor supply unit is a discharge nozzle of an elongated shape configured to move across a center portion of the substrate, and

the suction unit is a plurality of elongated suction nozzles that is installed at a front side and at a rear side of the elongated discharge nozzle in a direction intersecting an elongated direction of the discharge nozzle and removes the rinse solution by sucking the rinse solution supplied on the substrate while the vapor of the first processing solution is being supplied by the discharge nozzle when the substrate holder holding the substrate is rotated by the rotating unit.

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